JP5169435B2 - Secondary battery and manufacturing method thereof - Google Patents

Description

The present invention relates to a secondary battery and its preparation how comprises a nonaqueous cathode, an anode and an electrolyte.

  The lithium ion secondary battery is a secondary battery that uses the insertion and extraction of lithium in the charge / discharge reaction, and is greatly expected because it provides a higher energy density than a lead battery or a nickel cadmium battery.

  In lithium ion secondary batteries, carbon materials are widely used as negative electrode active materials. For example, a lithium ion secondary battery using a carbon material capable of inserting and extracting lithium ions such as coke, artificial graphite, and natural graphite has been proposed. In such a lithium ion secondary battery, since lithium does not exist in a metal state, formation of dendrite is suppressed, and battery life and safety can be improved. In particular, graphite-based carbon materials such as artificial graphite and natural graphite are expected as materials capable of improving the energy density per unit volume.

  Lithium ion secondary battery using graphite carbon material alone for negative electrode, or lithium ion used for negative electrode by mixing graphite carbon material and other negative electrode material capable of occluding and releasing lithium In the secondary battery, a carbonate ester that is generally used favorably in a lithium primary battery is used as a solvent for the electrolytic solution. However, when carbonic acid ester is used as the solvent of the electrolytic solution, the electrolytic solution is decomposed on the surface of the electrode during the charge / discharge process.

  Therefore, in order to suppress a decrease in charge / discharge efficiency, a decrease in cycle characteristics, and the like, for example, in Patent Document 1 and Patent Document 2, decomposition of the solvent is performed by decomposing the electrode surface earlier than the electrolytic solution to form a film. For example, a method of adding a cyclic carbonate having an unsaturated group such as vinylene carbonate or (4-vinyl) ethylene carbonate to an electrolytic solution has been proposed. In addition, in order to suppress a decrease in charge / discharge characteristics, Patent Documents 3 to 7 propose a method of adding a lactone derivative such as a derivative of γ-butyrolactone to the electrolytic solution.

Japanese Patent Laid-Open No. 5-74486 JP-A-8-45545 JP-A-11-54150 JP 2001-023684 A JP 2003-163031 A JP 2006-172775 A JP 2006-318760 A

  Recently, it has been demanded to further improve the battery capacity. For example, in order to further improve the battery capacity, silicon (Si) or tin (Sn) or the like is used for the negative electrode instead of the carbon material. It is being considered. Since the theoretical capacity of silicon (Si) (4199 mAh / g) and the theoretical capacity of tin (Sn) (994 mAh / g) are much larger than the theoretical capacity of graphite (372 mAh / g), the battery capacity is greatly improved. I can expect.

  For example, as described in Patent Document 8, in a secondary battery using a thin film of silicon (Si) or tin (Sn) as a negative electrode active material, even when lithium (Li) is occluded and released, Since the pulverization of the negative electrode active material is suppressed, a high discharge capacity can be obtained.

International Publication No. 01/031724 Pamphlet

  Patent Document 9 discloses a method for improving cycle characteristics when a metal, an element, an alloy, or a compound that can be combined with lithium such as tin (Sn) or silicon (Si) is used as the negative electrode active material. For example, a method has been proposed in which an electrolytic solution contains a cyclic or chain carbonate having halogen as a constituent element. The reason why the characteristics are improved by this method is presumed to be that a high ion permeability and high stability film is formed on the surface of the negative electrode during initial charging, so that the decomposition reaction of the electrolytic solution is suppressed. Is done.

JP 2004-47131 A

  However, when silicon (Si) or tin (Sn) is used as the negative electrode active material, the activity increases when lithium (Li) is occluded. When a dielectric solvent and a low-viscosity solvent such as a chain carbonate are used in combination, the chain carbonate is likely to be decomposed, and lithium is likely to be deactivated. In this case, if the pulverization of the negative electrode active material is not sufficiently suppressed in the charge / discharge process, the charge / discharge efficiency is lowered, and sufficient cycle characteristics and storage characteristics cannot be obtained.

  In Patent Document 9, a decomposition reaction of the electrolytic solution can be suppressed by containing a cyclic or chain carbonate having halogen as a constituent element in the electrolytic solution, but silicon (Si) or tin (Sn) is used as the negative electrode active material. ), Sufficient cycle characteristics are not obtained. Further, even when a carbon material is used as the negative electrode active material, it is required to further improve the cycle characteristics.

Accordingly, an object of the present invention is to provide a secondary battery and manufacturing how it is possible to improve the cycle characteristics.

（Ｒ１〜Ｒ５は水素または置換基である。Ｒ１〜Ｒ５は同一であっても、異なっていてもよく、結合していてもよい。Ｘは−ＯＭ、アミノ基またはハロゲン基である。Ｍは長周期型周期表における１族元素もしくは２族元素、または炭化水素基もしくはアルキルシリル基である。ｎ＝０〜４である。） In order to solve the above-described problem, the first invention
A positive electrode and a negative electrode opposed via a separator, and a non-aqueous electrolyte,
At least one of the positive electrode, the negative electrode, the separator, and the nonaqueous electrolyte is a secondary battery containing a compound represented by the formula (1).

(R1 to R5 are hydrogen or a substituent. R1 to R5 may be the same, different, or bonded. X is -OM, an amino group, or a halogen group. (It is a group 1 element or a group 2 element in a long-period periodic table, or a hydrocarbon group or an alkylsilyl group, where n = 0 to 4.)

（Ｒ１〜Ｒ５は水素または置換基である。Ｒ１〜Ｒ５は同一であっても、異なっていてもよく、結合していてもよい。Ｘは−ＯＭ、アミノ基またはハロゲン基である。Ｍは長周期型周期表における１族元素もしくは２族元素、または炭化水素基もしくはアルキルシリル基である。ｎ＝０〜４である。） The second invention is
A method for producing a secondary battery comprising a positive electrode and a negative electrode opposed via a separator, and a non-aqueous electrolyte,
In this method, the compound represented by the formula (1) is contained in at least one of the positive electrode, the negative electrode, the separator, and the nonaqueous electrolyte.

(R1 to R5 are hydrogen or a substituent. R1 to R5 may be the same, different, or bonded. X is -OM, an amino group, or a halogen group. (It is a group 1 element or a group 2 element in a long-period periodic table, or a hydrocarbon group or an alkylsilyl group, where n = 0 to 4.)

  In the first and second inventions, the compound represented by the formula (1) contained in at least one of the positive electrode, the negative electrode, the separator, and the non-aqueous electrolyte is the positive electrode and the negative electrode before the solvent is decomposed. Since the film is formed on the upper part or the part where the positive electrode and the negative electrode are in contact with the solvent, the decomposition reaction of the solvent can be suppressed.

  According to the first and second inventions, cycle characteristics can be improved by electrochemically stabilizing at least one of the positive electrode, the negative electrode, the separator, and the non-aqueous electrolyte.

  Embodiments of the present invention will be described below with reference to the drawings.

[First Embodiment]
The nonaqueous electrolyte according to the first embodiment of the present invention is, for example, a nonaqueous electrolyte solution containing a liquid solvent, an electrolyte salt dissolved in the solvent, and a compound represented by the formula (1). .

（Ｒ１〜Ｒ５は水素または置換基である。Ｒ１〜Ｒ５は同一であっても、異なっていてもよく、結合していてもよい。Ｘは−ＯＭ、アミノ基またはハロゲン基である。Ｍは長周期型周期表における１族元素もしくは２族元素、または炭化水素基もしくはアルキルシリル基である。ｎ＝０〜４である。）

(R1 to R5 are hydrogen or a substituent. R1 to R5 may be the same, different, or bonded. X is -OM, an amino group, or a halogen group. (It is a group 1 element or a group 2 element in a long-period periodic table, or a hydrocarbon group or an alkylsilyl group, where n = 0 to 4.)

  Examples of the substituent include a hydrocarbon group, an alkylsilyl group, a halogen group, a carboxyl group, a carboxylate metal base, an amide group, an acid halide group (—C (═O) —Z; Z is a halogen group), alkyl Examples thereof include a silyl ester group (—C (═O) —O— (alkylsilyl group)) or a derivative thereof. Specific examples of the hydrocarbon group include a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, and an alicyclic hydrocarbon group, and more specifically, a methyl group. , Ethyl group, propyl group, isopropyl group, butyl group, allyl group, phenyl group and the like. In addition, as the derivatives of the above-described groups, for example, a part of hydrogen of the hydrocarbon group is substituted with a carboxyl group, a carboxylate metal base, a halogen group, an amide group, an acid halide group, or an alkylsilyl ester group. Things.

  The compound represented by the formula (1) can form a film by decomposing on the electrode. Thereby, when it uses for a battery etc., since electrolyte solution is electrochemically stabilized, cycling characteristics can be improved. When the compound represented by the formula (1) is used in, for example, a lithium ion battery, it is considered that the ring is opened as shown in the reaction formula (I) to form a very stable film having low solubility. In addition, the compound represented by Formula (1) can acquire the same effect irrespective of stereoisomerism. That is, the S-isomer, R-isomer, or a mixture thereof, which is an enantiomer, can obtain the same effect, and any diastereomer or a mixture thereof can obtain the same effect.

  As a compound represented by Formula (1), the compound represented by Formula (2) which is n = 1 in Formula (1) is preferable. This is because when n = 1, the strain is small and the chemical stability is excellent.

（Ｒ１〜Ｒ５は水素または置換基である。Ｒ１〜Ｒ５は同一であっても、異なっていてもよく、結合していてもよい。Ｘは−ＯＭ、アミノ基またはハロゲン基である。Ｍは長周期型周期表における１族元素もしくは２族元素、または炭化水素基もしくはアルキルシリル基である。）

(R1 to R5 are hydrogen or a substituent. R1 to R5 may be the same, different, or bonded. X is -OM, an amino group, or a halogen group. It is a group 1 element or a group 2 element in a long-period type periodic table, or a hydrocarbon group or an alkylsilyl group.)

  The compound represented by the formula (1) is a compound represented by the formula (3) in which X = -OM and M = Li, Mg, or a hydrocarbon group in the formula (1) because more excellent characteristics are obtained. A compound represented by formula (4), a compound represented by formula (5), or a compound represented by formula (5) is preferred. This is because the case where M = Li or Mg is stable in the battery, and the case where M = hydrocarbon group does not deteriorate the battery characteristics even if the reaction occurs in the battery.

（Ｒ１〜Ｒ５は水素または置換基である。Ｒ１〜Ｒ５は同一であっても、異なっていてもよく、結合していてもよい。ｎ＝０〜４である。）

(R1 to R5 are hydrogen or a substituent. R1 to R5 may be the same or different, and may be bonded. N = 0 to 4)

（Ｒ１〜Ｒ５は水素または置換基である。Ｒ１〜Ｒ５は同一であっても、異なっていてもよく、結合していてもよい。ｎ＝０〜４である。）

(R1 to R5 are hydrogen or a substituent. R1 to R5 may be the same or different, and may be bonded. N = 0 to 4)

（Ｒ１〜Ｒ５は水素または置換基である。Ｒ１〜Ｒ５は同一であっても、異なっていてもよく、結合していてもよい。Ｒ６は炭化水素基である。ｎ＝０〜４である。）

(R1 to R5 are hydrogen or a substituent. R1 to R5 may be the same or different and may be bonded. R6 is a hydrocarbon group. N = 0 to 4. .)

  As the compound represented by the formula (1), in the formula (1), n = 1, X = −OM, and M = Li, Mg, or a hydrocarbon group, the formula (6), the formula (7) ) Or a compound represented by formula (8) is particularly preferred.

（Ｒ１〜Ｒ５は水素または置換基である。Ｒ１〜Ｒ５は同一であっても、異なっていてもよく、結合していてもよい。）

(R1 to R5 are hydrogen or a substituent. R1 to R5 may be the same, different, or bonded.)

（Ｒ１〜Ｒ５は水素または置換基である。Ｒ１〜Ｒ５は同一であっても、異なっていてもよく、結合していてもよい。）

(R1 to R5 are hydrogen or a substituent. R1 to R5 may be the same, different, or bonded.)

（Ｒ１〜Ｒ５は水素または置換基である。Ｒ１〜Ｒ５は同一であっても、異なっていてもよく、結合していてもよい。Ｒ６は炭化水素基である。）

(R1 to R5 are hydrogen or a substituent. R1 to R5 may be the same or different and may be bonded. R6 is a hydrocarbon group.)

  Moreover, as a compound represented by Formula (1), since the characteristic outstanding similarly to the compound represented by Formula (3)-(5) is acquired, it is a formula (X = amino group or a halogen group ( It may be a compound represented by 9) or a compound represented by formula (10), or a compound represented by formula (11) wherein X = -OM and M = alkylsilyl group.

（Ｒ１〜Ｒ５は水素または置換基である。Ｒ１〜Ｒ５は同一であっても、異なっていてもよく、結合していてもよい。Ｒ７およびＲ８は水素またはアルキル基である。Ｒ７およびＲ８は同一であっても、異なっていてもよく、結合していてもよい。ｎ＝０〜４である。）

(R1 to R5 are hydrogen or a substituent. R1 to R5 may be the same, different, or bonded. R7 and R8 are hydrogen or an alkyl group. R7 and R8 are (It may be the same, may be different, or may be bonded. N = 0 to 4.)

（Ｒ１〜Ｒ５は水素または置換基である。Ｒ１〜Ｒ５は同一であっても、異なっていてもよく、結合していてもよい。Ｙはハロゲン基である。ｎ＝０〜４である。）

(R1 to R5 are hydrogen or a substituent. R1 to R5 may be the same or different, and may be bonded to each other. Y is a halogen group. N = 0 to 4. )

（Ｒ１〜Ｒ５は水素または置換基である。Ｒ１〜Ｒ５は同一であっても、異なっていてもよく、結合していてもよい。Ｒ９〜Ｒ１１は水素またはアルキル基である。Ｒ９〜Ｒ１１は同一であっても、異なっていてもよく、結合していてもよい。ｎ＝０〜４である。）

(R1 to R5 are hydrogen or a substituent. R1 to R5 may be the same or different, and may be bonded. R9 to R11 are hydrogen or an alkyl group. (It may be the same, may be different, or may be bonded. N = 0 to 4.)

  The compound represented by the formula (1) includes a compound represented by the formula (12) or the formula (13) in which n = 1 and X = amino group or halogen group in the formula (1), n A compound represented by the formula (14) in which X = 1, X = −OM, and M = alkylsilyl group may be used.

（Ｒ１〜Ｒ５は水素または置換基である。Ｒ１〜Ｒ５は同一であっても、異なっていてもよく、結合していてもよい。Ｒ７およびＲ８は水素またはアルキル基である。Ｒ７およびＲ８は同一であっても、異なっていてもよく、結合していてもよい。）

(R1 to R5 are hydrogen or a substituent. R1 to R5 may be the same, different, or bonded. R7 and R8 are hydrogen or an alkyl group. R7 and R8 are They may be the same, different, or combined.)

（Ｒ１〜Ｒ５は水素または置換基である。Ｒ１〜Ｒ５は同一であっても、異なっていてもよく、結合していてもよい。Ｙはハロゲン基である。）

(R1 to R5 are hydrogen or a substituent. R1 to R5 may be the same or different, and may be bonded. Y is a halogen group.)

（Ｒ１〜Ｒ５は水素または置換基である。Ｒ１〜Ｒ５は同一であっても、異なっていてもよく、結合していてもよい。Ｒ９〜Ｒ１１は水素またはアルキル基である。Ｒ９〜Ｒ１１は同一であっても、異なっていてもよく、結合していてもよい。）

(R1 to R5 are hydrogen or a substituent. R1 to R5 may be the same or different, and may be bonded. R9 to R11 are hydrogen or an alkyl group. They may be the same, different, or combined.)

  More specifically, examples of the compound represented by the formula (1) include 5-oxotetrahydrofuran-2-carboxylic acid represented by the formula (15) and isocitrate-γ represented by the formula (16). -Lactone, camphanic acid represented by formula (17), 4,5-dicarboxypentadecanolactone represented by formula (18), and compounds represented by formula (19) to formula (48) It is done.

  Examples of the solvent include ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, γ-butyrolactone, γ-valerolactone, 1,2-dimethoxyethane, tetrahydrofuran, and 2-methyl. Tetrahydrofuran, tetrahydropyran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,3-dioxane, 1,4-dioxane, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, Methyl isobutyrate, methyl trimethylacetate, ethyl trimethylacetate, acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, 3-methoxypropionitrile, N, N-dimethylformamide, N-methylpyrrolidinone, N-methyl Oxazolidinone, N, N′-dimethylimidazolidinone, nitromethane, nitroethane, sulfolane, trimethyl phosphate, dimethyl sulfoxide, and the like can be used. This is because, in an electrochemical device such as a battery provided with an electrolytic solution, excellent capacity, cycle characteristics and storage characteristics can be obtained. These may be used alone or in combination of two or more.

  Among them, it is preferable to use a solvent containing at least one member selected from the group consisting of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate. This is because a sufficient effect can be obtained. In this case, in particular, ethylene carbonate or propylene carbonate having a high viscosity (high dielectric constant) solvent (for example, relative dielectric constant ε ≧ 30) and dimethyl carbonate having a low viscosity solvent (for example, viscosity ≦ 1 mPa · s). It is preferable to use a mixture containing diethyl carbonate or ethyl methyl carbonate. This is because the dissociation property of the electrolyte salt and the ion mobility are improved, so that a higher effect can be obtained.

  The solvent further includes cyclic carbonate derivatives such as 4-fluoro-1,3dioxolan-2-one (FEC) and 4,5-difluoro-1,3-dioxolan-2-one (DFEC). Is preferred. This is because the cycle characteristics can be further improved.

  Furthermore, as a solvent, it is preferable that the cyclic carbonate compound which has unsaturated bonds, such as vinylene carbonate (VC) and vinyl ethylene carbonate (VEC), is further included. This is because the cycle characteristics can be further improved.

  Further, the solvent preferably further contains a cyclic sultone derivative such as propane sultone and propene sultone (PRS). This is because the cycle characteristics can be further improved.

  Furthermore, the solvent preferably further contains an acid anhydride such as succinic anhydride and 2-sulfobenzoic anhydride. This is because the cycle characteristics can be further improved.

Examples of lithium salts that are electrolyte salts include lithium hexafluorophosphate (LiPF ₆ ), lithium tetrafluoroborate (LiBF ₄ ), lithium perchlorate (LiClO ₄ ), lithium hexafluoroarsenate (LiAsF ₆ ), and trifluoromethane. Lithium sulfonate (CF ₃ SO ₃ Li), bis (trifluoromethanesulfonyl) imido lithium [(CF ₃ SO ₂ ) ₂ NLi] (LiTFSI), tris (trifluoromethanesulfonyl) methyl lithium [(CF ₃ SO ₂ ) ₃ CLi ], lithium bis (oxalato) borate [LiB (C ₂ O _{4) 2]} (LiBOB), such as 1,3-perfluoropropanedisulfonylimide lithium of the formula (49) can be used. Any one of these may be used, or two or more thereof may be mixed and used.

  Further, as the non-aqueous electrolyte, a gel electrolyte in which a non-aqueous electrolyte is held in a polymer compound may be used. The gel electrolyte is not particularly limited as long as the ion conductivity is 1 mS / cm or more at room temperature, and the composition and the structure of the polymer compound are not particularly limited. Since the solvent, electrolyte salt, and compound represented by the formula (1) contained in the nonaqueous electrolytic solution are as described above, detailed description thereof is omitted.

  Examples of the polymer compound include polyacrylonitrile, polyvinylidene fluoride, a copolymer of polyvinylidene fluoride and polyhexafluoropropylene, polytetrafluoroethylene, polyhexafluoropropylene, polyethylene oxide, polypropylene oxide, polyphosphazene, poly Siloxane, polyvinyl acetate, polyvinyl alcohol, polymethyl methacrylate, polyacrylic acid, polymethacrylic acid, styrene-butadiene rubber, nitrile-butadiene rubber, polystyrene, or polycarbonate can be used. In particular, from the viewpoint of electrochemical stability, it is preferable to use a polymer compound having a polyacrylonitrile, polyvinylidene fluoride, polyhexafluoropropylene, or polyethylene oxide structure.

  Here, the term “solvent” does not mean only a liquid solvent, but a concept that widely dissociates electrolyte salts and has ion conductivity. Therefore, when using what has ion conductivity for a high molecular compound, the high molecular compound is also contained in a solvent.

  The nonaqueous electrolyte according to the first embodiment of the present invention can be suitably used for a secondary battery using a material containing at least one of silicon (Si) and tin (Sn) as a constituent element for the negative electrode, It can be particularly suitably used for a non-aqueous electrolyte battery using a material containing silicon (Si) for the negative electrode. In a secondary battery using a material containing at least one of silicon (Si) and tin (Sn) as a constituent element for the negative electrode, the negative electrode has high activity and the electrolyte is easily decomposed, and a carbon material is used for the negative electrode. This is more effective than the case because the cycle characteristics tend to deteriorate.

  Using the nonaqueous electrolyte according to the first embodiment of the present invention, for example, secondary batteries such as lithium batteries having various shapes and sizes can be manufactured.

  A first example of a secondary battery using a nonaqueous electrolyte according to the first embodiment of the present invention will be described. FIG. 1 shows an example of the configuration of a first example of a secondary battery according to the first embodiment of the invention. This secondary battery has a so-called coin shape, and is, for example, a non-aqueous electrolyte secondary battery, for example, a lithium ion secondary battery.

  As shown in FIG. 1, the nonaqueous electrolyte battery includes a positive electrode 2, an outer can 6 that accommodates the positive electrode 2, a negative electrode 4, an outer cup 5 that accommodates the negative electrode 4, a positive electrode 2, and a negative electrode 4. And a gasket 7 that insulates the separator 3, the outer cup 5, and the outer can 6.

  The positive electrode 2 has a structure in which a positive electrode active material layer 2B is provided on a positive electrode current collector 2A.

  The positive electrode current collector 2A is made of a metal material such as net-like or foil-like aluminum (Al), nickel (Ni), or stainless steel (SUS). The positive electrode active material layer 2B includes, for example, any one or more of positive electrode materials capable of inserting and extracting lithium (Li) as an electrode reactant as a positive electrode active material. Accordingly, a conductive agent and a binder may be included.

As a positive electrode material capable of inserting and extracting lithium, for example, a lithium-containing compound is preferable. This is because a high energy density can be obtained. Examples of the lithium-containing compound include a composite oxide containing lithium (Li) and a transition metal element, and a phosphate compound containing lithium (Li) and a transition metal element. Especially, what contains at least 1 sort (s) of the group which consists of cobalt (Co), nickel (Ni), manganese (Mn), and iron (Fe) as a transition metal element is preferable. This is because a higher voltage can be obtained. The chemical formula is represented by, for example, Li _x M1O ₂ or Li _y M2PO ₄ . In the formula, M1 and M2 represent one or more transition metal elements. The values of x and y vary depending on the charge / discharge state, and are generally 0.05 ≦ x ≦ 1.10 and 0.05 ≦ y ≦ 1.10.

Examples of the composite oxide containing lithium (Li) and a transition metal element include lithium cobalt composite oxide (Li _x CoO ₂ ), lithium nickel composite oxide (Li _x NiO ₂ ), and lithium nickel cobalt composite oxide ( _{Li x Ni 1-z Co z} O 2 (z <1)), a lithium nickel cobalt manganese complex oxide _{(Li x Ni (1-vw} ) Co v Mn w O 2 (v + w <1)), or spinel structure And lithium manganese composite oxide (LiMn ₂ O ₄ ). Among these, a composite oxide containing cobalt (Co) is preferable. This is because a high capacity can be obtained and excellent cycle characteristics can be obtained. Examples of the phosphoric acid compound containing lithium and a transition metal element include a lithium iron phosphate compound (LiFePO ₄ ) or a lithium iron manganese phosphate compound (LiFe _1-u Mn _u PO ₄ (u <1)). Is mentioned.

  In addition, as a positive electrode material capable of inserting and extracting lithium (Li), for example, an oxide such as titanium oxide, vanadium oxide or manganese dioxide, a disulfide such as titanium disulfide or molybdenum sulfide, Examples thereof also include chalcogenides such as niobium selenide and conductive polymers such as sulfur, polyaniline or polythiophene.

  Examples of the binder include synthetic rubber such as styrene butadiene rubber, fluorine rubber or ethylene propylene diene, and a polymer material such as polyvinylidene fluoride (PVdF). These may be single and multiple types may be mixed. Moreover, as a electrically conductive agent, a carbon material is mentioned, for example. More specifically, for example, carbon black or graphite can be used as the conductive agent.

  The outer can 6 is a container made of a conductive metal, and is made of a metal such as stainless steel (SUS) or aluminum (Al).

  The negative electrode 4 has a structure in which a negative electrode active material layer 4B is provided on a negative electrode current collector 4A.

  The anode current collector 4A is preferably made of a metal material having good electrochemical stability, electrical conductivity, and mechanical strength. Examples of such a metal material include copper (Cu), nickel (Ni), and stainless steel (SUS), and among these, copper (Cu) is preferable. This is because high electrical conductivity can be obtained.

  In particular, the metal material described above preferably contains one or more metal elements that do not form an intermetallic compound with lithium (Li), which is an electrode reactant. When an intermetallic compound is formed with lithium (Li), for example, since it is easily affected by stress due to expansion and contraction of the negative electrode active material layer 4B during charge and discharge, the current collecting property may be lowered, and the negative electrode active material This is because the layer 4B may peel off from the negative electrode current collector 4A. Examples of such metal elements include copper (Cu), nickel (Ni), titanium (Ti), iron (Fe), and chromium (Cr).

  Moreover, it is preferable that the metal material mentioned above contains any 1 type, or 2 or more types of the metal element alloyed with the negative electrode active material layer 4B. This is because the adhesion between the negative electrode current collector 4A and the negative electrode active material layer 4B is improved, so that the negative electrode active material layer 4B is difficult to peel from the negative electrode current collector 4A. As a metal element that does not form an intermetallic compound with lithium (Li) and is alloyed with the negative electrode active material layer 4B, for example, when the negative electrode active material layer 4B contains silicon (Si) as a negative electrode active material, Examples include copper (Cu), nickel (Ni), and iron (Fe). These metal elements are also preferable from the viewpoints of strength and conductivity.

  The negative electrode current collector 4A may have a single layer structure or a multilayer structure. When the negative electrode current collector 4A has a multilayer structure, for example, a layer adjacent to the negative electrode active material layer 4B is made of a metal material alloyed therewith, and a non-adjacent layer is made of another metal material. preferable.

  The surface of the negative electrode current collector 4A is preferably roughened. This is because the adhesion between the negative electrode current collector 4A and the negative electrode active material layer 4B is improved by a so-called anchor effect. In this case, the surface of the negative electrode current collector 4A only needs to be roughened at least in a region facing the negative electrode active material layer 4B. Examples of the roughening method include a method of forming fine particles by electrolytic treatment. This electrolytic treatment is a method of forming irregularities by forming fine particles on the surface of the negative electrode current collector 4A by an electrolytic method in an electrolytic bath. The copper foil produced by the electrolytic method including the copper foil roughened by this electrolytic treatment is generally called “electrolytic copper foil”.

  The negative electrode active material layer 4B includes any one or more of negative electrode materials capable of inserting and extracting lithium (Li) as an electrode reactant as a negative electrode active material. Other materials such as the above-described conductive agent or binder may be included. Examples of the negative electrode material capable of inserting and extracting lithium (Li) include carbon materials, metal oxides, and polymer compounds. Examples of the carbon material include graphitizable carbon, non-graphitizable carbon having a (002) plane spacing of 0.37 nm or more, and graphite having a (002) plane spacing of 0.340 nm or less. More specifically, there are pyrolytic carbons, cokes, graphites, glassy carbons, organic polymer compound fired bodies, carbon fibers or activated carbon. Of these, cokes include pitch coke, needle coke, and petroleum coke. Organic polymer compound fired bodies are carbonized by firing polymer compounds such as phenol resins and furan resins at an appropriate temperature. What you did. In addition, examples of the metal oxide include iron oxide, ruthenium oxide, and molybdenum oxide, and examples of the polymer compound include polyacetylene and polypyrrole.

  Further, the negative electrode active material layer 4B, for example, as a negative electrode active material, a simple substance, an alloy and a compound of a metal element capable of occluding and releasing lithium (Li) as an electrode reactant, and occluding lithium (Li). And at least one negative electrode material selected from the group consisting of simple metals, alloys and compounds of metalloid elements that can be released. Thereby, a high energy density can be obtained. Furthermore, you may make it use together with the carbon material mentioned above. The carbon material has very little change in the crystal structure that occurs during charging and discharging. For example, if used together with the negative electrode material described above, a high energy density can be obtained and excellent cycle characteristics can be obtained. This is preferable because it can function as a conductive agent. Note that in this specification, alloys include those composed of one or more metal elements and one or more metalloid elements in addition to those composed of two or more metal elements. Moreover, the nonmetallic element may be included. Some of the structures include a solid solution, a eutectic (eutectic mixture), an intermetallic compound, or a mixture of two or more of them.

  Examples of metal elements or metalloid elements constituting the negative electrode material include magnesium (Mg), boron (B), aluminum (Al), gallium (Ga), indium (In), silicon (Si), germanium (Ge), Tin (Sn), lead (Pb), bismuth (Bi), cadmium (Cd), silver (Ag), zinc (Zn), hafnium (Hf), zirconium (Zr), yttrium (Y), palladium (Pd) or Platinum (Pt) is mentioned. These may be crystalline or amorphous.

As the alloy or compound of these metal elements or metalloid elements, for example, those represented by the chemical formula Ma _s Mb _t Li _u or a chemical formula Ma _p Mc _q Md _r,. In these chemical formulas, Ma represents at least one of metal elements and metalloid elements capable of forming an alloy with lithium (Li), and Mb represents metal elements other than lithium (Li) and Ma and metalloid elements. At least one of nonmetallic elements, and Md represents at least one of metallic elements and metalloid elements other than Ma. The values of s, t, u, p, q, and r are s> 0, t ≧ 0, u ≧ 0, p> 0, q> 0, and r ≧ 0, respectively.

  Among these, the negative electrode material is preferably a simple substance, alloy or compound of a group 14 metal element or metalloid element in the long-period periodic table, and particularly preferably at least of silicon (Si) and tin (Sn). It is a material containing one kind as a constituent element. That is, it is a simple substance, alloy or compound of silicon (Si), or a simple substance, alloy or compound of tin (Sn). A material containing at least one of silicon (Si) and tin (Sn) as a constituent element has a large ability to occlude and release lithium (Li). Depending on the combination, the material of the negative electrode 4 can be compared with that of conventional graphite. This is because the energy density can be increased.

Specific examples of such alloys or compounds include SiB ₄ , SiB ₆ , Mg ₂ Si, Ni ₂ Si, TiSi ₂ , MoSi ₂ , CoSi ₂ , NiSi ₂ , CaSi ₂ , CrSi ₂ , Cu ₅ Si. FeSi ₂ , MnSi ₂ , NbSi ₂ , TaSi ₂ , VSi ₂ , WSi ₂ , ZnSi ₂ , SiC, Si ₃ N ₄ , Si ₂ N ₂ O, SiO _v (0 <v ≦ 2), SnO _w (0 < w ≦ 2), SnSiO ₃ , LiSiO, LiSnO, Mg ₂ Sn, or an alloy containing tin (Sn) and cobalt (Co).

  Among these, as this negative electrode material, tin (Sn), cobalt (Co), and carbon (C) are included as constituent elements, and the carbon content is 9.9 mass% or more and 29.7 mass% or less. And the ratio Co / (Sn + Co) of cobalt (Co) with respect to the sum total of tin (Sn) and cobalt (Co) is preferably 30% by mass or more and 70% by mass or less. This is because a high energy density can be obtained in such a composition range, and excellent cycle characteristics can be obtained.

  This CoSnC-containing material may further contain other constituent elements as necessary. Examples of other constituent elements include silicon (Si), iron (Fe), nickel (Ni), chromium (Cr), indium (In), niobium (Nb), germanium (Ge), titanium (Ti), and molybdenum. (Mo), aluminum (Al), phosphorus (P), gallium (Ga) or bismuth (Bi) are preferable and may contain two or more. This is because the capacity or cycle characteristics can be further improved.

  The CoSnC-containing material has a phase containing tin (Sn), cobalt (Co), and carbon (C), and this phase has a low crystallinity or an amorphous structure. Preferably it is. This phase is a reaction phase capable of reacting with lithium, whereby excellent cycle characteristics can be obtained. The half-value width of the diffraction peak obtained by X-ray diffraction of this phase is 1.0 ° or more at a diffraction angle 2θ when CuKα ray is used as the specific X-ray and the drawing speed is 1 ° / min. Is preferred. This is because lithium (Li) is occluded and released more smoothly, and the reactivity with the nonaqueous electrolyte is reduced.

  Whether a diffraction peak obtained by X-ray diffraction corresponds to a reaction phase capable of reacting with lithium (Li) is determined by comparing X-ray diffraction charts before and after electrochemical reaction with lithium. It can be easily judged. For example, if the position of the diffraction peak changes before and after the electrochemical reaction with lithium (Li), it corresponds to a reaction phase capable of reacting with lithium (Li). In this case, for example, a diffraction peak of a low crystalline or amorphous reaction phase is observed between 2θ = 20 ° and 50 °. This low crystalline or amorphous reaction phase contains, for example, each of the above-described constituent elements, and is considered to be low crystallized or amorphous mainly by carbon (C).

  Note that the CoSnC-containing material may have a phase containing a simple substance or a part of each constituent element in addition to a low crystalline or amorphous phase.

  In particular, in a CoSnC-containing material, it is preferable that at least a part of carbon that is a constituent element is bonded to a metal element or a metalloid element that is another constituent element. This is because aggregation or crystallization of tin (Sn) or the like is suppressed.

  As a measuring method for examining the bonding state of elements, for example, X-ray photoelectron spectroscopy (XPS) can be cited. This XPS irradiates the sample surface with soft X-rays (Al-Kα ray or Mg-Kα ray is used in a commercial apparatus), and measures the kinetic energy of photoelectrons jumping out of the sample surface. To elemental composition in the region of several nanometers and the bonding state of the elements.

  The binding energy of the core orbital electrons of the element changes in a first approximation in correlation with the charge density on the element. For example, when the charge density of the carbon element decreases due to an interaction with an element present in the vicinity, the outer electrons such as 2p electrons decrease, so the 1s electron of the carbon element exerts a strong binding force from the shell. Will receive. That is, the binding energy increases as the charge density of the element decreases. In XPS, when the binding energy increases, the peak shifts to a high energy region.

  In XPS, if the peak of carbon 1s orbital (C1s) is graphite, it appears at 284.5 eV in an energy calibrated apparatus so that the peak of 4f orbital (Au4f) of gold atom is obtained at 84.0 eV. . Moreover, if it is surface contamination carbon, it will appear at 284.8 eV. On the other hand, when the charge density of the carbon element is high, for example, when it is bonded to an element more positive than carbon, the C1s peak appears in a region lower than 284.5 eV. That is, when at least part of the carbon contained in the CoSnC-containing material is bonded to a metal element or a metalloid element that is another constituent element, the peak of the synthetic wave of C1s obtained for the CoSnC-containing material is 284. Appears in a region lower than 5 eV.

  When performing XPS measurement, it is preferable to lightly sputter the surface with an argon ion gun attached to the XPS apparatus when the surface is covered with surface-contaminated carbon. When a negative electrode having a CoSnC-containing material to be measured is present in the secondary battery, the secondary battery is disassembled and the negative electrode is taken out and then washed with a volatile solvent such as dimethyl carbonate. This is for removing the low-volatile solvent and the electrolyte salt present on the negative electrode surface. These samplings are preferably performed under an inert atmosphere.

  In XPS measurement, for example, the peak of C1s is used to correct the energy axis of the spectrum. Usually, since surface-contaminated carbon exists on the surface of the substance, the C1s peak of the surface-contaminated carbon is set to 284.8 eV, and this is used as an energy standard. In the XPS measurement, the waveform of the peak of C1s is obtained as a form including the surface contamination carbon peak and the carbon peak in the CoSnC-containing material. For example, by analyzing using commercially available software, The surface contamination carbon peak is separated from the carbon peak in the CoSnC-containing material. In the waveform analysis, the position of the main peak existing on the lowest bound energy side is used as the energy reference (284.8 eV).

  This CoSnC-containing material can be formed by, for example, a method in which a mixture obtained by mixing raw materials of each constituent element is melted in an electric furnace, a high-frequency induction furnace, an arc melting furnace or the like and then solidified. Further, various atomizing methods such as gas atomization or water atomization, various roll methods, methods utilizing mechanochemical reactions such as mechanical alloying method or mechanical milling method, and the like may be used. Among these, a method using a mechanochemical reaction is preferable. This is because the CoSnC-containing material has a low crystalline or amorphous structure. In the method using the mechanochemical reaction, for example, a manufacturing apparatus such as a planetary ball mill or an attritor can be used.

  The raw material may be a mixture of individual constituent elements, but an alloy is preferably used for some constituent elements other than carbon (C). This is because, by adding carbon to such an alloy and synthesizing it by a method using a mechanical alloying method, a low crystalline or amorphous structure is obtained, and the reaction time is shortened. The raw material may be in the form of powder or a block.

  In addition to this CoSnC-containing material, a CoSnFeC-containing material having tin (Sn), cobalt (Co), iron (Fe), and carbon (C) as constituent elements is also preferable. The composition of the CoSnFeC-containing material can be arbitrarily set. For example, as a composition when the content of iron (Fe) is set to be small, the content of carbon (C) is 9.9 mass% or more and 29.7 mass% or less, and the content of iron (Fe) is 0 The ratio of cobalt (Co) to the total of tin (Sn) and cobalt (Co) (Co / (Sn + Co)) is 30% by mass or more and 70% by mass or less. Is preferred. Further, for example, as a composition when the content of iron (Fe) is set to be large, the content of carbon (C) is 11.9 mass% or more and 29.7 mass% or less, tin (Sn) and cobalt ( The total ratio of cobalt (Co) and iron (Fe) to the total of (Co) and iron (Fe) ((Co + Fe) / (Sn + Co + Fe)) is 26.4% by mass or more and 48.5% by mass or less, cobalt ( The ratio of cobalt (Co) to the total of (Co) and iron (Fe) (Co / (Co + Fe)) is preferably 9.9 mass% or more and 79.5 mass% or less. This is because a high energy density can be obtained in such a composition range. Since the crystallinity of the CoSnFeC-containing material, the method for measuring the bonding state of elements, the formation method, and the like are the same as those of the above-described CoSnC-containing material, detailed description thereof is omitted.

  As a negative electrode material capable of inserting and extracting lithium (Li), silicon (Si) simple substance, alloy or compound, tin (Sn) simple substance, alloy or compound, one or more of them The negative electrode active material layer 4B using a material having at least a part of the phase is formed using, for example, a gas phase method, a liquid phase method, a thermal spraying method, a coating method, a firing method, or two or more of these methods. The

  A negative electrode active material layer 4B using a simple substance, an alloy or a compound of silicon (Si), a simple substance, an alloy or a compound of tin (Sn), or a material having one or more phases thereof at least in part. In the case of forming by using a vapor phase method, a liquid phase method, a thermal spraying method, a coating method or a firing method, or two or more of these methods, the negative electrode current collector 4A and the negative electrode active material layer 4B are at least at the interface. Some are alloyed, which is preferable. Furthermore, heat treatment may be performed in a vacuum atmosphere or a non-oxidizing atmosphere to form an alloy. Specifically, the constituent element of the negative electrode current collector 4A may diffuse into the negative electrode active material layer 4B at the interface between them, or the constituent element of the negative electrode active material layer 4B diffuses into the negative electrode current collector 4A. These constituent elements may be diffused with each other. This is because breakage due to expansion and contraction of the negative electrode active material layer 4B during charging / discharging is suppressed, and electronic conductivity between the negative electrode current collector 4A and the negative electrode active material layer 4B can be improved. .

  As the vapor phase method, for example, physical deposition method or chemical deposition method, specifically, vacuum deposition method, sputtering method, ion plating method, laser ablation method, thermal chemical vapor deposition (CVD) Or plasma chemical vapor deposition. As the liquid phase method, a known method such as electrolytic plating or electroless plating can be used. The application method is, for example, a method in which a particulate negative electrode active material is mixed with a binder and then dispersed in a solvent and applied. The baking method is, for example, a method in which a heat treatment is performed at a temperature higher than the melting point of a binder or the like after being applied by a coating method. A known method can also be used for the firing method, for example, an atmospheric firing method, a reactive firing method, or a hot press firing method.

  The exterior cup 5 is a container made of a conductive metal that accommodates the negative electrode 4 and serves as an external negative electrode. Specifically, the outer cup 5 uses, for example, a metal container made of aluminum (Al), stainless steel (SUS), iron (Fe) plated with nickel (Ni), or the like.

  The separator 3 separates the positive electrode 2 and the negative electrode 4 and allows lithium ions in the non-aqueous electrolyte to pass through while preventing a short circuit of current due to contact between both electrodes. The separator 3 is made of a microporous membrane having a large number of minute holes. Here, the microporous membrane is a resin membrane having a large number of micropores having an average pore diameter of about 5 μm or less. Moreover, as the separator 3, what has been used for the conventional battery as a material can be utilized. Among them, a microporous film made of polypropylene, polyolefin, or the like that is excellent in short-circuit prevention effect and can improve battery safety by a shutdown effect is used.

  The gasket 7 has a structure in which it is integrated into the exterior cup 5 and is made of, for example, an organic resin such as polypropylene. The gasket 7 insulates the outer can 6 serving as the external positive electrode from the outer cup 5 serving as the external negative electrode, and prevents leakage of the nonaqueous electrolyte filled in the outer cup 5 and the outer can 6. To work.

  Next, the manufacturing method of the 1st example of a secondary battery is demonstrated. The positive electrode 2 is produced, for example, as described below. First, for example, a positive electrode active material, a conductive agent, and a binder are dispersed in a non-aqueous solvent to prepare a positive electrode mixture coating solution. Next, this positive electrode mixture coating solution is uniformly applied to a positive electrode current collector 2A in the form of a metal foil such as an aluminum (Al) foil, dried, and then compression molded to form the positive electrode active material layer 2B. Form. Thereby, the positive electrode 2 is obtained.

  The negative electrode 4 is produced, for example, as described below. First, for example, a negative electrode active material and a binder are dispersed in a non-aqueous solvent or the like to prepare a negative electrode mixture coating solution. This negative electrode mixture coating solution is uniformly applied to a metal foil-like negative electrode current collector 4A such as a copper (Cu) foil, dried, and then compressed to form the negative electrode active material layer 4B. Thereby, the negative electrode 4 is obtained.

  Next, the positive electrode 2 is accommodated in the outer can 6, the negative electrode 4 is accommodated in the outer cup 5, and the separator 3 made of a polypropylene porous film or the like is disposed between the positive electrode 2 and the negative electrode 4. Thereby, the nonaqueous electrolyte battery has an internal structure in which the positive electrode 2, the separator 3, and the negative electrode 4 are sequentially laminated.

  Next, the nonaqueous electrolyte is poured into the outer can 6 and the outer cup 5, and the outer can 6 and the outer cup 5 are fixed via the gasket 7. The secondary battery shown in FIG. 1 is obtained as described above.

  Next, a second example of the secondary battery using the nonaqueous electrolyte according to the first embodiment of the present invention will be described. FIG. 2 is a cross-sectional view showing a configuration of a second example of the secondary battery.

  This secondary battery is, for example, a non-aqueous electrolyte secondary battery, for example, a lithium ion secondary battery. This non-aqueous electrolyte battery is a so-called cylindrical type, and a pair of strip-like positive electrode 21 and strip-like negative electrode 22 are wound through a separator 23 in a substantially hollow cylindrical battery can 11. A wound electrode body 20 is provided. The separator 23 is impregnated with a non-aqueous electrolyte that is a liquid non-aqueous electrolyte. The battery can 11 is made of, for example, iron (Fe) plated with nickel (Ni), and has one end closed and the other end open. Inside the battery can 11, a pair of insulating plates 12 and 13 are arranged perpendicular to the winding peripheral surface so as to sandwich the winding electrode body 20.

  At the open end of the battery can 11, a battery lid 14, a safety valve mechanism 15 provided inside the battery lid 14 and a heat sensitive resistance element (Positive Temperature Coefficient; PTC element) 16 are interposed via a gasket 17. It is attached by caulking, and the inside of the battery can 11 is sealed.

  The battery lid 14 is made of, for example, the same material as the battery can 11. The safety valve mechanism 15 is electrically connected to the battery lid 14 via the heat sensitive resistance element 16, and the disk plate 15A is reversed when the internal pressure of the battery exceeds a certain level due to an internal short circuit or external heating. Thus, the electrical connection between the battery lid 14 and the wound electrode body 20 is cut off. When the temperature rises, the heat sensitive resistance element 16 limits the current by increasing the resistance value and prevents abnormal heat generation due to a large current. The gasket 17 is made of, for example, an insulating material, and asphalt is applied to the surface.

  The wound electrode body 20 is wound around a center pin 24, for example. A positive electrode lead 25 made of aluminum (Al) or the like is connected to the positive electrode 21 of the spirally wound electrode body 20, and a negative electrode lead 26 made of nickel or the like is connected to the negative electrode 22. The positive electrode lead 25 is electrically connected to the battery lid 14 by being welded to the safety valve mechanism 15, and the negative electrode lead 26 is welded to and electrically connected to the battery can 11.

  FIG. 3 is an enlarged cross-sectional view showing a part of the spirally wound electrode body 20 shown in FIG. Hereinafter, the positive electrode 21, the negative electrode 22, and the separator 23 constituting the nonaqueous electrolyte battery will be sequentially described with reference to FIG.

  The positive electrode 21 has, for example, a structure in which a positive electrode active material layer 21B is provided on both surfaces of a positive electrode current collector 21A having a pair of opposed surfaces. Although not shown, the positive electrode active material layer 21B may be provided on only one surface of the positive electrode current collector 21A. The positive electrode current collector 21A has the same configuration as that of the positive electrode current collector 2A of the first example described above, and is made of, for example, a metal foil such as an aluminum foil.

  The positive electrode active material layer 21B includes, for example, a positive electrode material capable of inserting and extracting lithium (Li). If necessary, a conductive agent such as graphite and polyvinylidene fluoride (PVDF) are used. It is configured to contain a binder. Since the positive electrode material capable of inserting and extracting lithium is the same as that described in the first example, detailed description thereof is omitted.

  The negative electrode 22 has, for example, a structure in which a negative electrode active material layer 22B is provided on both surfaces of a negative electrode current collector 22A having a pair of opposed surfaces. Although not shown, the negative electrode current collector 22A may have a region where the negative electrode active material layer 22B is provided only on one surface. The negative electrode current collector 22A has the same configuration as that of the negative electrode current collector 4A of the first example described above, and is configured by, for example, a metal foil such as a copper foil.

  The negative electrode active material layer 22B includes, for example, a negative electrode material capable of inserting and extracting lithium (Li), and includes a binder similar to that of the positive electrode active material layer 21B as necessary. It is configured. Since the negative electrode material capable of inserting and extracting lithium (Li) is the same as that described in the first example, detailed description thereof is omitted.

  Since the separator 23 is the same as the separator 3 described in the first example, detailed description thereof is omitted.

  Next, an example of a manufacturing method of the second example of the secondary battery will be described. First, for example, a positive electrode active material, a conductive agent, and a binder are mixed to prepare a positive electrode mixture, and the positive electrode mixture is dispersed in a solvent such as N-methyl-2-pyrrolidone to obtain a paste-like material. A positive electrode mixture slurry is prepared. Next, the positive electrode mixture slurry is applied to the positive electrode current collector 21A, the solvent is dried, and the positive electrode active material layer 21B is formed by compression molding using a roll press or the like. Thereby, the positive electrode 21 is obtained.

  Further, for example, a negative electrode active material and a binder are mixed to prepare a negative electrode mixture, and this negative electrode mixture is dispersed in a solvent such as N-methyl-2-pyrrolidone to obtain a paste-like negative electrode mixture slurry Is made. Next, the negative electrode mixture slurry is applied to the negative electrode current collector 22A, the solvent is dried, and the negative electrode active material layer 22B is formed by compression molding using a roll press or the like. Thereby, the negative electrode 22 is obtained.

  Next, the positive electrode lead 25 is attached to the positive electrode current collector 21A by welding or the like, and the negative electrode lead 26 is attached to the negative electrode current collector 22A by welding or the like. After that, the positive electrode 21 and the negative electrode 22 are laminated via the separator 23 and then wound in the longitudinal direction to produce the wound electrode body 20. Subsequently, the center pin 24 is inserted into the winding center portion of the winding electrode body 20. Subsequently, the spirally wound electrode body 20 is housed in the battery can 11 while being sandwiched between the pair of insulating plates 12 and 13, the tip of the positive electrode lead 25 is welded to the safety valve mechanism 15, and the tip of the negative electrode lead 26 is attached. Weld to battery can 11. Subsequently, a non-aqueous electrolyte is injected into the battery can 11 and impregnated in the separator 23. After that, the battery lid 14, the safety valve mechanism 15, and the heat sensitive resistance element 16 are fixed to the opening end of the battery can 11 by caulking through the gasket 17. Thereby, the secondary battery shown in FIG. 2 and FIG. 3 is obtained.

  Next, a third example of the secondary battery will be described. FIG. 4 is a cross-sectional view showing a configuration example of the third example of the secondary battery. In this secondary battery, a wound electrode body 30 to which a positive electrode lead 31 and a negative electrode lead 32 are attached is accommodated in a film-like exterior member 40, and can be reduced in size, weight, and thickness. ing.

  The positive electrode lead 31 and the negative electrode lead 32 are led out from the inside of the exterior member 40 toward the outside, for example, in the same direction. The positive electrode lead 31 and the negative electrode lead 32 are each made of a metal material such as aluminum (Al), copper (Cu), nickel (Ni), or stainless steel (SUS), and each have a thin plate shape or a mesh shape. Yes.

  The exterior member 40 is made of, for example, a rectangular aluminum laminated film in which a nylon film, an aluminum foil, and a polyethylene film are bonded together in this order. The exterior member 40 is disposed, for example, so that the polyethylene film side and the wound electrode body 30 face each other, and the outer edge portions are in close contact with each other by fusion or an adhesive. An adhesive film 41 is inserted between the exterior member 40 and the positive electrode lead 31 and the negative electrode lead 32 to prevent intrusion of outside air. The adhesion film 41 is made of a material having adhesion to the positive electrode lead 31 and the negative electrode lead 32, for example, a polyolefin resin such as polyethylene, polypropylene, modified polyethylene, or modified polypropylene.

  The exterior member 40 may be made of a laminated film having another structure, a polymer film such as polypropylene, or a metal film instead of the above-described aluminum laminated film.

  FIG. 5 is a cross-sectional view taken along line II of the spirally wound electrode body 30 shown in FIG. The wound electrode body 30 is obtained by stacking and winding a positive electrode 33 and a negative electrode 34 with a separator 35 and an electrolyte layer 36 interposed therebetween, and the outermost peripheral portion is protected by a protective tape 37.

  The positive electrode 33 has a structure in which a positive electrode active material layer 33B is provided on one or both surfaces of a positive electrode current collector 33A. The negative electrode 34 has a structure in which a negative electrode active material layer 34B is provided on one surface or both surfaces of a negative electrode current collector 34A, and the negative electrode active material layer 34B and the positive electrode active material layer 33B are arranged to face each other. Yes. The configurations of the positive electrode current collector 33A, the positive electrode active material layer 33B, the negative electrode current collector 34A, the negative electrode active material layer 34B, and the separator 35 are the positive electrode current collectors 2A and 21A described in the first example or the second example, respectively. Since the positive electrode active material layers 2B and 21B, the negative electrode current collectors 4A and 22A, the negative electrode active material layers 4B and 22B, and the separators 3 and 23 are the same, detailed description thereof is omitted.

  The electrolyte layer 36 includes the above-described non-aqueous electrolyte and a polymer compound serving as a holding body that holds the non-aqueous electrolyte, and is a so-called gel-like non-aqueous electrolyte. The gel electrolyte layer 36 is preferable because high ion conductivity can be obtained and battery leakage can be prevented. The electrolyte layer 36 may be used as it is without holding the non-aqueous electrolyte in the polymer compound.

  Next, an example of the manufacturing method of the 3rd example of a secondary battery is demonstrated. First, a precursor solution containing a solvent, an electrolyte salt, a compound represented by the formula (1), a polymer compound, and a mixed solvent is applied to each of the positive electrode 33 and the negative electrode 34, and the mixed solvent is volatilized. Thus, the electrolyte layer 36 is formed. After that, the positive electrode lead 31 is attached to the end of the positive electrode current collector 33A by welding, and the negative electrode lead 32 is attached to the end of the negative electrode current collector 34A by welding.

  Next, the positive electrode 33 and the negative electrode 34 on which the electrolyte layer 36 is formed are laminated via a separator 35 to form a laminated body, and then the laminated body is wound in the longitudinal direction, and a protective tape 37 is attached to the outermost peripheral portion. The wound electrode body 30 is formed by bonding. Finally, for example, the wound electrode body 30 is sandwiched between the exterior members 40, and the outer edges of the exterior members 40 are sealed and sealed by heat fusion or the like. At that time, the adhesion film 41 is inserted between the positive electrode lead 31 and the negative electrode lead 32 and the exterior member 40. Thereby, the secondary battery shown in FIGS. 4 and 5 is obtained.

  Further, this secondary battery may be manufactured as follows. First, the positive electrode 33 and the negative electrode 34 are prepared as described above, and after the positive electrode lead 31 and the negative electrode lead 32 are attached to the positive electrode 33 and the negative electrode 34, the positive electrode 33 and the negative electrode 34 are stacked via the separator 35 and wound. The wound electrode body 30 is formed by rotating and bonding the protective tape 37 to the outermost periphery. Next, the wound electrode body 30 is sandwiched between the exterior members 40, and the outer peripheral edge except for one side is heat-sealed to form a bag shape and housed inside the exterior member 40. Subsequently, a solvent, an electrolyte salt, a compound represented by the formula (1), a monomer that is a raw material of the polymer compound, a polymerization initiator, and other materials such as a polymerization inhibitor as necessary. An electrolyte composition is prepared and injected into the exterior member 40.

  After injecting the electrolyte composition, the opening of the exterior member 40 is heat-sealed and sealed in a vacuum atmosphere. Next, the electrolyte layer 36 is formed by applying heat to polymerize the monomer to obtain a polymer compound. Thus, the secondary battery shown in FIGS. 4 and 5 is obtained.

  Next, another embodiment of the present invention will be described.

[Second Embodiment]
FIG. 6 shows a cross-sectional configuration of the negative electrode in the second embodiment of the present invention. The negative electrode 100 is used for an electrochemical device such as a secondary battery, for example, a negative electrode current collector 101 having a pair of surfaces, a negative electrode active material layer 102 provided on the negative electrode current collector 101, And a coating 103 provided on the negative electrode active material layer 102. The negative electrode active material layer 102 may be provided on both sides of the negative electrode current collector 101 or may be provided only on one side. The same applies to the coating 103. Hereinafter, a case where the electrode reactant that is occluded and released in the negative electrode 100 is lithium (Li) will be described.

  The negative electrode current collector 101 has, for example, the same configuration as the negative electrode current collectors 4A, 22A, and 34B of the first to third examples of the secondary battery in the first embodiment. Description is omitted.

  The negative electrode active material layer 102 includes one or more negative electrode materials capable of inserting and extracting lithium as a negative electrode active material. Since this negative electrode material is the same as that described in the first example of the secondary battery in the first embodiment, detailed description thereof is omitted.

  In the negative electrode active material layer 102, the negative electrode active material made of the negative electrode material described above has a plurality of particles. That is, the negative electrode active material layer 102 has a plurality of negative electrode active material particles. The negative electrode active material particles are formed by, for example, the above-described vapor phase method. However, the negative electrode active material particles may be formed by a method other than the gas phase method.

  When the negative electrode active material particles are formed by a vapor phase method, the negative electrode active material particles may have a single layer structure formed through a single deposition process, or a plurality of deposition processes. You may have the multilayered structure formed through these. However, in the case where the negative electrode active material particles are formed by a vapor deposition method with high heat during deposition, the negative electrode active material particles preferably have a multilayer structure. By performing the deposition process of the negative electrode material in a plurality of times (the negative electrode material is sequentially formed and deposited), the negative electrode current collector 101 is exposed to high heat as compared with the case where the deposition process is performed once. This is because the time required for heat treatment is shortened and it is difficult to receive thermal damage.

  The negative electrode active material particles grow, for example, from the surface of the negative electrode current collector 101 in the thickness direction of the negative electrode active material layer 102 and are connected to the negative electrode current collector 101 at the base. In this case, it is preferable that the negative electrode active material particles are formed by a vapor phase method and alloyed at least at a part of the interface with the negative electrode current collector 101 as described above. Specifically, the constituent element of the negative electrode current collector 101 may be diffused into the negative electrode active material particles at the interface between them, or the constituent element of the negative electrode active material particles is diffused into the negative electrode current collector 101. Alternatively, the constituent elements of both may diffuse to each other.

  In particular, the negative electrode active material layer 102 preferably has an oxide-containing film that covers the surface of the negative electrode active material particles (a region in contact with the nonaqueous electrolytic solution) as necessary. When the negative electrode 100 is used in an electrochemical device such as a secondary battery equipped with a non-aqueous electrolyte, the oxide-containing film functions as a protective film against the non-aqueous electrolyte. This is because the decomposition reaction of the electrolytic solution is suppressed. This oxide-containing film may cover a part of the surface of the negative electrode active material particles, or may cover the whole.

  This oxide-containing film contains an oxide of a metal element or a metalloid element. Examples of the metal element or metalloid oxide include oxides such as aluminum (Al), silicon (Si), zinc (Zn), germanium (Ge), and tin (Sn). Among these, the oxide-containing film preferably contains at least one oxide selected from the group consisting of silicon (Si), germanium (Ge), and tin (Sn). It preferably contains an oxide. This is because the entire surface of the negative electrode active material particles can be easily covered and an excellent protective function can be obtained. Of course, the oxide-containing film may contain an oxide other than the above-described oxides.

  This oxide-containing film can be formed by using one or more methods such as a gas phase method or a liquid phase method. Examples of the vapor phase method in this case include a vapor deposition method, a sputtering method, or a CVD method. Examples of the liquid phase method include a liquid phase deposition method, a sol-gel method, a polysilazane method, an electrodeposition method, a coating method, or a coating method. Examples include dip coating. Among these, the liquid phase method is preferable, and the liquid phase precipitation method is more preferable. This is because the surface of the negative electrode active material particles can be easily covered over a wide range. In the liquid phase precipitation method, first, fluoride ions generated from a fluoride complex in a solution containing a fluoride complex of a metal element or a semi-metal group element and a dissolved species that easily coordinates fluoride ions as an anion scavenger. Is captured by an anion scavenger to deposit an oxide of a metal element or a semi-metal group element so that the surface of the negative electrode active material particles is coated. Thereafter, the oxide-containing film is formed by washing with water and drying.

  In addition, the negative electrode active material layer 102 preferably includes a metal material that does not alloy with lithium (Li) in the gaps between the negative electrode active material particles and the gaps in the particles as necessary. Since a plurality of negative electrode active material particles are bound via a metal material, and the expansion and contraction of the negative electrode active material layer 102 are suppressed by the presence of the metal material in the gaps described above, the negative electrode 100 is a secondary battery. This is because the cycle characteristics can be improved when used in electrochemical devices such as the above.

  This metal material has, for example, a metal element that does not alloy with lithium (Li) as a constituent element. Examples of such a metal element include at least one selected from the group consisting of iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), and copper (Cu). Co) is preferred. This is because the metal material can easily enter the gaps described above and an excellent binding function can be obtained. Of course, the metal material may have a metal element other than the metal elements described above. However, the “metal material” mentioned here represents a broad concept including not only a simple substance but also an alloy and a metal compound. The metal material is formed by, for example, a gas phase method or a liquid phase method, and among them, a liquid phase method such as an electrolytic plating method or an electroless plating method is preferable, and an electrolytic plating method is more preferable. This is because the metal material can easily enter the gaps described above and the formation time can be shortened.

  Note that the negative electrode active material layer 102 may include only one or both of the above-described oxide-containing film and metal material. However, in order to further improve the cycle characteristics of an electrochemical device such as a secondary battery, it is preferable to have both.

  Here, the detailed configuration of the negative electrode 100 will be described with reference to FIGS. 7 to 10, the coating 103 is omitted.

  First, the case where the negative electrode active material layer 102 has an oxide-containing film together with a plurality of negative electrode active material particles will be described. FIG. 7 schematically shows a cross-sectional structure of the negative electrode 100 according to the second embodiment, and FIG. 8 schematically shows a cross-sectional structure of the negative electrode of the reference example. 7 and 8 show a case where the negative electrode active material particles have a single layer structure.

  In the negative electrode 100, as shown in FIG. 7, when a negative electrode material is deposited on the negative electrode current collector 101 by a vapor phase method such as a vapor deposition method, a plurality of negative electrode actives are formed on the negative electrode current collector 101. Material particles 201 are formed. In this case, when the surface of the negative electrode current collector 101 is roughened and a plurality of protrusions (for example, fine particles formed by electrolytic treatment) exist on the surface, the negative electrode active material particles 201 have the protrusions described above. Each of the negative electrode active material particles 201 is arranged on the negative electrode current collector 101 and connected to the negative electrode current collector 101 at the root. After that, for example, when the oxide-containing film 202 is formed on the surface of the negative electrode active material particle 201 by a liquid phase method such as a liquid phase precipitation method, the oxide-containing film 202 substantially covers the surface of the negative electrode active material particle 201. The entire surface is covered, and in particular, a wide range from the top of the negative electrode active material particle 201 to the root is covered. This wide covering state by the oxide-containing film 202 is a characteristic obtained when the oxide-containing film 202 is formed by a liquid phase method. That is, when the oxide-containing film 202 is formed by a liquid phase method, the covering action extends not only to the top of the negative electrode active material particles 201 but also to the root, so that the base is covered with the oxide-containing film 202.

  On the other hand, in the negative electrode of the reference example, as shown in FIG. 8, for example, after a plurality of negative electrode active material particles 201 are formed by a vapor phase method, the oxide is similarly formed by a vapor phase method such as a vapor deposition method. When the containing film 203 is formed, the oxide-containing film 203 covers only the tops of the negative electrode active material particles 201. This narrow covering state by the oxide-containing film 203 is a characteristic obtained when the oxide-containing film 203 is formed by a vapor phase method. In other words, when the oxide-containing film 203 is formed by a vapor phase method, the covering action does not reach the root of the negative electrode active material particles 201, so that the base is not covered by the oxide-containing film 203.

  Note that although FIG. 7 illustrates the case where the negative electrode active material layer 102 is formed by a vapor phase method, a plurality of negative electrode active materials are similarly formed when the negative electrode active material layer 102 is formed by a sintering method or the like. An oxide-containing film is formed so as to cover the entire surface of the particles.

  Next, a case where the negative electrode active material layer 102 includes a metal material that does not alloy with lithium together with a plurality of negative electrode active material particles will be described. FIG. 9 shows an enlarged cross-sectional structure of the negative electrode 100. (A) is a scanning electron microscope (SEM) photograph (secondary electron image), and (B) is an SEM shown in (A). It is a schematic picture of the statue. FIG. 9 shows a case where a plurality of negative electrode active material particles have a multilayer structure in the particles.

  When the negative electrode active material particles 201 have a multilayer structure, a plurality of gaps 204 are generated in the negative electrode active material layer 102 due to the dense structure, the multilayer structure, and the surface structure of the plurality of negative electrode active material particles 201. Yes. The gap 204 mainly includes two types of gaps 204A and 204B classified according to the cause of occurrence. The gap 204 </ b> A is generated between adjacent negative electrode active material particles 201, and the gap 204 </ b> B is generated between layers in the negative electrode active material particles 201.

  Note that a void 205 may be formed on the exposed surface (outermost surface) of the negative electrode active material particles 201. The void 205 is a void generated between the protrusions as a whisker-like fine protrusion (not shown) is generated on the surface of the negative electrode active material particle 201. The void 205 may occur over the entire exposed surface of the negative electrode active material particle 201 or may occur only in part. However, since the above-described whisker-like protrusions are generated on the surface every time the negative electrode active material particles 201 are formed, the voids 205 are generated not only on the exposed surface of the negative electrode active material particles 201 but also between the layers. There is.

  FIG. 10 shows another cross-sectional structure of the negative electrode and corresponds to FIG. The negative electrode active material layer 102 includes a metal material 206 that does not alloy with lithium (Li) in the gaps 204A and 204B. In this case, only one of the gaps 204A and 204B may have the metal material 206, but it is preferable that both have the metal material 206. This is because a higher effect can be obtained.

  This metal material 206 enters the gap 204 </ b> A between the adjacent negative electrode active material particles 201. Specifically, when the negative electrode active material particles 201 are formed by a vapor phase method or the like, as described above, the negative electrode active material particles 201 grow for each protrusion existing on the surface of the negative electrode current collector 101. A gap 204 </ b> A is generated between the adjacent negative electrode active material particles 201. Since the gap 204A causes a decrease in the binding property of the negative electrode active material layer 102, the above-described gap 204A is filled with the metal material 206 in order to improve the binding property. In this case, it is sufficient that a part of the gap 204A is filled, but the larger the filling amount, the better. This is because the binding property of the negative electrode active material layer 102 is further improved. The filling amount of the metal material 206 is preferably 20% or more, more preferably 40% or more, and further preferably 80% or more.

  In addition, the metal material 206 enters the gap 204 </ b> B in the negative electrode active material particles 201. Specifically, when the negative electrode active material particles 201 have a multilayer structure, a gap 204B is generated between the layers. Since the gap 204B causes a decrease in the binding property of the negative electrode active material layer 102 as in the case of the gap 204A, the gap 204B is filled with the metal material 206 in order to improve the binding property. ing. In this case, it is sufficient that a part of the gap 204B is filled, but a larger filling amount is preferable. This is because the binding property of the negative electrode active material layer 102 is further improved.

  Note that the negative electrode active material layer 102 has a beard-like fine protrusion (not shown) generated on the exposed surface of the uppermost negative electrode active material particle 201 in order to suppress adverse effects on the performance of the electrochemical device. The gap 205 may have a metal material 206. Specifically, when the negative electrode active material particles 201 are formed by a vapor phase method or the like, fine whisker-like protrusions are formed on the surface thereof, and voids 205 are generated between the protrusions. The voids 205 increase the surface area of the negative electrode active material particles 201 and increase the amount of irreversible coating film formed on the surface of the negative electrode active material particles 201, which may cause a decrease in the degree of progress of the electrode reaction. Therefore, the metal material 206 is embedded in the above-described gap 205 in order to suppress a decrease in the progress of the electrode reaction. In this case, it is sufficient that a part of the gap 205 is buried, but it is preferable that the amount to be buried is larger. This is because a decrease in the degree of progress of the electrode reaction is further suppressed. In FIG. 10, the fact that the metal material 206 is scattered on the surface of the uppermost negative electrode active material particle 201 indicates that the above-described fine protrusions are present at the spot. Of course, the metal material 206 does not necessarily have to be scattered on the surface of the negative electrode active material particle 201, and may cover the entire surface.

  In particular, the metal material 206 that has entered the gap 204B also functions to fill the gap 205 in each layer. Specifically, when the negative electrode active material particles 201 are deposited a plurality of times, the fine protrusions described above are generated on the surface of the negative electrode active material particles 201 every time the negative electrode active material particles 201 are deposited. From this, the metal material 206 is not only filled in the gap 204B in each layer, but also fills the gap 205 in each layer.

  Before confirmation, in FIGS. 9 and 10, the case where the negative electrode active material particles 201 have a multilayer structure and both the gaps 204 </ b> A and 204 </ b> B exist in the negative electrode active material layer 2 has been described. The substance layer 102 has a metal material 206 in the gaps 204A and 204B. On the other hand, when the negative electrode active material particle 201 has a single-layer structure and only the gap 204A exists in the negative electrode active material layer 102, the negative electrode active material layer 102 has the metal material 206 only in the gap 204A. It will have. Of course, since the gap 205 is generated in both cases, the gap 205 includes the metal material 206 in either case.

  The film 103 contains the compound represented by the formula (1) described above. By providing the coating 103 containing the compound represented by the formula (1), the chemical stability of the negative electrode 100 can be improved. Therefore, when the negative electrode 100 is used in an electrochemical device such as a secondary battery, lithium is efficiently inserted and extracted from the negative electrode 100, and the negative electrode 100 is made of another substance (for example, a nonaqueous electrolyte in a secondary battery). ), The cycle characteristics can be improved.

  The coating 103 may be provided so as to cover the entire surface of the negative electrode active material layer 102, or may be provided so as to cover a part of the surface thereof. In addition, a part of the coating 103 may enter the negative electrode active material layer 102.

  Since the compound represented by the formula (1) is the same as that contained in the nonaqueous electrolyte in the first embodiment, a detailed description thereof will be omitted. A compound represented by (3), a compound represented by formula (4), a compound represented by formula (6) or a compound represented by formula (7) is preferred.

  The film 103 is a salt of a group 1 metal element or a group 2 element salt in the long-period periodic table (excluding those corresponding to the compound represented by the formula (1) together with the compound represented by the formula (1). ) May be contained. This is because the film resistance can be suppressed, so that the cycle characteristics can be further improved when the negative electrode is used in an electrochemical device such as a secondary battery.

Examples of the salt of the Group 1 metal element or the Group 2 element in the long-period periodic table include, for example, a Group 1 metal element or a Group 2 element carbonate or halide salt in the long-period periodic table. Examples thereof include borate, phosphate and sulfonate. More specifically, for example, lithium carbonate (Li ₂ CO ₃ ), lithium fluoride (LiF), lithium tetraborate (Li ₂ B ₄ O ₇ ), lithium metaborate (LiBO ₂ ), lithium pyrophosphate (Li ₄ P ₂ O ₇ ), lithium tripolyphosphate (Li ₅ P ₃ O ₁₀ ), lithium orthosilicate (Li ₄ SiO ₄ ), lithium metasilicate (Li ₂ SiO ₃ ), dilithium ethanedisulfonate, dilithium propanedisulfonate , Dilithium sulfoacetate, dilithium sulfopropionate, dilithium sulfobutanoate, dilithium sulfobenzoate, dilithium succinate, trilithium sulfosuccinate, dilithium squarate, magnesium ethanedisulfonate, magnesium propanedisulfonate, sulfoacetic acid Magnesium, magnesium sulfopropionate, Magnesium sulfobutanoate, magnesium sulfobenzoate, magnesium succinate, trimagnesium disulfosuccinate, calcium ethanedisulfonate, calcium propanedisulfonate, calcium sulfoacetate, calcium sulfopropionate, calcium sulfobutanoate, calcium sulfobenzoate, calcium succinate , Tricalcium disulfosuccinate and the like. These may be single and multiple types may be mixed.

  Examples of the method for forming the film 103 include a liquid phase method such as a coating method, a dipping method, or a dip coating method, and a vapor phase method such as a vapor deposition method, a sputtering method, or a CVD (Chemical Vapor Deposition) method. Is mentioned. These methods may be used alone, or two or more methods may be used. Among these, as the liquid phase method, it is preferable to form the film 103 using a solution containing the compound represented by the formula (1). More specifically, for example, in the immersion method, the negative electrode current collector 101 on which the negative electrode active material layer 102 is formed is immersed in a solution containing the compound represented by the formula (1). In the application method, the above-described solution is applied to the negative electrode active material layer 102. Thereby, the favorable film 103 with high chemical stability is easily formed. Examples of the solvent for dissolving the compound represented by the formula (1) include a highly polar solvent such as water.

  Next, an example of a method for manufacturing the negative electrode 100 will be described. First, the negative electrode active material layers 102 are formed on both surfaces of the negative electrode current collector 101. In the case of forming the negative electrode active material layer 102, a negative electrode material is deposited on the surface of the negative electrode current collector 101 by a vapor phase method such as a vapor deposition method to form a plurality of negative electrode active material particles. After that, if necessary, an oxide-containing film is formed by a liquid phase method such as a liquid phase deposition method, or a metal material is formed by a liquid phase method such as an electrolytic plating method. Finally, a film 103 is formed on the surface of the negative electrode active material layer 102. In the case of forming the coating 103, for example, an aqueous solution having a concentration of 1% by weight to 5% by weight is prepared as a solution containing the compound represented by the formula (1) to form the negative electrode active material layer 102. The negative electrode current collector 101 is immersed in the solution for several seconds, then pulled up and dried at room temperature. Alternatively, the above solution is prepared, applied to the surface of the negative electrode active material layer 102, and dried. Thereby, the negative electrode 100 is obtained.

  In the negative electrode 100 and the manufacturing method thereof according to the second embodiment of the present invention, since the coating 103 containing the compound represented by the formula (1) is formed on the negative electrode active material layer 102, the coating 103 is formed. Compared with the case where it does not, the chemical stability of the negative electrode 100 can be improved. Therefore, when this negative electrode 100 is used in an electrochemical device such as a secondary battery, lithium is efficiently occluded and released in the negative electrode 100, and the negative electrode 100 reacts with other substances such as a non-aqueous electrolyte. It becomes difficult. For this reason, cycle characteristics can be improved. In this case, the film 103 is formed using a solution containing the compound represented by the formula (1), and more specifically, a simple process such as an immersion process or a coating process is used. As compared with the case where a method requiring special environmental conditions such as a reduced pressure environment is used, a favorable coating 103 can be easily formed.

  In addition, when the negative electrode active material layer 102 includes a plurality of negative electrode active material particles, cycle characteristics can be further improved if the negative electrode active material layer 102 includes a metal material that does not alloy with the oxide-containing film or the electrode reactant. it can.

  Using the negative electrode (negative electrode 100) and the manufacturing method thereof according to the second embodiment of the present invention, for example, secondary batteries such as lithium batteries having various shapes and sizes can be manufactured. The negative electrode 100 can be used, for example, as the negative electrodes 4, 22, and 34 in the first to third examples of the secondary battery described in the first embodiment. When used as the negative electrode in the first to third examples of the secondary battery, the non-aqueous electrolyte (non-aqueous electrolyte) used in the first to third examples has the formula (1) The compound represented may or may not be contained, but higher effects can be obtained when it is contained.

  Note that in the second embodiment, the case where the negative electrode 100 includes the coating 103 has been described. However, the negative electrode current collector 101 and the negative electrode active material layer 102 described above can be formed even when the coating 103 is not formed. It can be used as the negative electrode current collectors 4A, 22A, 34A and the negative electrode active material layers 4B, 22B, 34B of the first to third examples of the secondary battery using the nonaqueous electrolyte in the embodiment. That is, the negative electrode active material layer has a negative electrode active material particle and has an oxide film covering the surface of the negative electrode active material particle, or a plurality of negative electrode active material particles and an electrode reaction in a gap between the negative electrode active material particles The negative electrode having a metal material that does not alloy with the substance (Li) can be used as the negative electrodes 4, 22, and 34 of the first to third examples of the secondary battery using the nonaqueous electrolyte in the first embodiment. .

[Third Embodiment]
FIG. 11 shows a cross-sectional configuration of the positive electrode according to the third embodiment of the present invention. The positive electrode 300 is used for an electrochemical device such as a secondary battery, for example, and includes a positive electrode current collector 301 having a pair of surfaces, a positive electrode active material layer 302 provided on the positive electrode current collector 301, A coating 303 provided on the positive electrode active material layer 302. The positive electrode active material layer 302 may be provided on both surfaces of the positive electrode current collector 301 or may be provided on only one surface. The same applies to the coating 303. Hereinafter, the case where lithium is used as the electrode reactant that is occluded and released in the positive electrode 300 will be described.

  The positive electrode current collector 301 is similar to, for example, the positive electrode current collectors 2A, 21A, and 33A of the first to third examples of the secondary battery in the first embodiment, and detailed description thereof is omitted.

  The positive electrode active material layer 302 includes one or more positive electrode materials capable of inserting and extracting lithium as a positive electrode active material. Since this positive electrode material is the same as the positive electrode material described in the first to third examples of the secondary battery in the first embodiment, detailed description thereof is omitted.

  The coating 303 contains the compound represented by the above formula (1). By providing the coating 303 containing the compound represented by the formula (1), the chemical stability of the positive electrode 300 can be improved. Therefore, when this positive electrode 300 is used in an electrochemical device such as a secondary battery, lithium is efficiently occluded and released in the positive electrode 300, and the positive electrode 300 is made of another substance (for example, a nonaqueous electrolyte in a secondary battery). ), The cycle characteristics can be improved.

  The coating 303 may be provided so as to cover the entire surface of the positive electrode active material layer 302, or may be provided so as to cover a part of the surface thereof. In addition, a part of the coating 303 may enter the inside of the positive electrode active material layer 302.

  Since the compound represented by the formula (1) is the same as that contained in the nonaqueous electrolyte in the first embodiment, a detailed description thereof will be omitted. A compound represented by (3), a compound represented by formula (4), a compound represented by formula (6) or a compound represented by formula (7) is preferred.

  Since the method for forming the film 303 is the same as the method for forming the film 103 described in the second embodiment, a detailed description thereof is omitted.

  Next, an example of a method for manufacturing the positive electrode 300 will be described. First, the positive electrode active material layer 302 is formed on both surfaces of the positive electrode current collector 301. When forming this positive electrode active material layer 302, it forms similarly to the positive electrode active material layers 2B, 21B, and 33B. Finally, the film 303 is formed. The formation of the film 303 is the same as the case of forming the film 103 in the second embodiment, and thus detailed description thereof is omitted. Thereby, the positive electrode 300 is obtained.

  In the positive electrode 300 and the manufacturing method thereof according to the third embodiment of the present invention, the coating 303 containing the compound represented by the formula (1) is formed on the positive electrode active material layer 302. Therefore, the coating 303 is formed. Compared with the case where it does not, the chemical stability of the positive electrode 300 can be improved. Therefore, when this positive electrode 300 is used in an electrochemical device such as a secondary battery, lithium (Li) is efficiently occluded and released in the positive electrode 300, and the positive electrode 100 is made of another substance such as a non-aqueous electrolyte. It becomes difficult to react with. For this reason, cycle characteristics can be improved. In this case, the film 303 is formed using a solution containing the compound represented by the formula (1), and more specifically, a simple process such as an immersion process or a coating process is used. Compared with the case where a method that requires special environmental conditions such as a reduced pressure environment is used, a good coating 303 can be easily formed.

  Using the positive electrode (positive electrode 300) and the manufacturing method thereof according to the third embodiment of the present invention, for example, secondary batteries such as lithium batteries having various shapes and sizes can be manufactured. The positive electrode 300 can be used, for example, as the positive electrodes 2, 21, 33 in the first to third examples of the secondary battery described in the first embodiment. When used as the positive electrode in the first to third examples of the secondary battery, the non-aqueous electrolyte (non-aqueous electrolyte) used in the first to third examples has the formula (1) The compound represented may or may not be contained, but higher effects can be obtained when it is contained. Moreover, you may use the positive electrode 300 in combination with the negative electrode in 2nd Embodiment in the 1st-3rd example of the secondary battery in 1st Embodiment.

[Fourth Embodiment]
FIG. 12 shows a cross-sectional configuration of the separator according to the fourth embodiment of the present invention. The separator 400 is used in, for example, a secondary battery, and separates the positive electrode and the negative electrode and allows the electrode reactant to pass through while preventing a short circuit of current due to contact between the two electrodes. The separator 400 includes a microporous membrane 401 having a pair of surfaces and a coating 402 provided on the pair of surfaces of the microporous membrane 401. The coating 402 may be provided on both sides of the microporous membrane 401 or may be provided only on one side.

  The microporous membrane 401 is the same as the microporous membrane constituting the separators 3, 23, 35 of the first to third examples of the secondary battery in the first embodiment, for example. Omitted.

  The coating 402 contains the compound represented by the formula (1) described above. By providing the coating film 402 containing the compound represented by the formula (1), chemical stability can be improved. Therefore, when this separator 400 is used for a secondary battery or the like, the positive electrode and the negative electrode are less likely to react with other substances (for example, the nonaqueous electrolyte in the secondary battery), so that the cycle characteristics can be improved.

  This coating film 402 may be provided so as to cover the entire surface of the microporous film 401 or may be provided so as to cover a part of the surface thereof. Further, a part of the coating 402 may be impregnated inside the microporous membrane 401.

  Since the compound represented by the formula (1) is the same as that contained in the nonaqueous electrolyte in the first embodiment, a detailed description thereof will be omitted. A compound represented by (3), a compound represented by formula (4), a compound represented by formula (6) or a compound represented by formula (7) is preferred.

  The method of forming the coating 402 is the same as the method of forming the coatings 103 and 303 described in the second and third embodiments, and detailed description thereof is omitted.

  In the separator 400 and the manufacturing method thereof according to the fourth embodiment of the present invention, the coating 402 containing the compound represented by the formula (1) is formed on the microporous membrane 401. When used in a battery, the positive electrode and the negative electrode are less likely to react with other substances such as a non-aqueous electrolyte. For this reason, cycle characteristics can be improved compared with the case where the coating 401 is not formed. In this case, the coating film 402 is formed using a solution containing the compound represented by the formula (1), and more specifically, a simple process such as an immersion process or a coating process is used. As compared with the case where a method that requires special environmental conditions such as the environment is used, a favorable coating 402 can be easily formed.

  Using the separator and the manufacturing method thereof according to the fourth embodiment of the present invention, for example, secondary batteries such as lithium batteries having various shapes and sizes can be manufactured. The separator 400 can be used, for example, as the separators 3, 23, and 35 in the first to third examples of the secondary battery described in the first embodiment. When used as a separator in the first to third examples of the secondary battery, the non-aqueous electrolyte (non-aqueous electrolyte) used in the first to third examples has the formula (1) The compound represented may or may not be contained, but higher effects can be obtained when it is contained. In addition, separator 400 is used in the first to third examples of the secondary battery in the first embodiment together with at least one of negative electrode 100 and positive electrode 300 in the second and third embodiments. Also good.

  The present invention has been described with reference to the first to fourth embodiments. In the present invention, at least one of the above-described nonaqueous electrolyte, negative electrode, positive electrode, and separator is represented by the formula (1). As long as it contains a compound. That is, as described above, when the positive electrode and the negative electrode contain the compound represented by the formula (1), a film containing the compound represented by the formula (1) is formed on the positive electrode active material layer and the negative electrode active material layer. However, the present invention is not limited to this, and the coating may not be formed as long as the compound represented by the formula (1) is included. Moreover, although the case where the compound represented by Formula (1) melt | dissolved in a nonaqueous electrolyte as a case where a nonaqueous electrolyte contains the compound represented by Formula (1) was demonstrated, in that case, Formula (1) Part of the compound represented by 1) may be dissolved, or all may be dispersed. When the separator contains the compound represented by the formula (1), a film containing the compound represented by the formula (1) may be formed on one side or both sides thereof.

  The constituent element containing the compound represented by the formula (1) may be any one of the positive electrode, the negative electrode, the separator, and the nonaqueous electrolyte, but preferably two or more are included, and all are included. It is preferable that This is because the decomposition reaction of the nonaqueous electrolyte can be further suppressed. Among these, if only one component including the compound represented by formula (1) is selected, a separator is preferable to the positive electrode, a non-aqueous electrolyte is more preferable than the separator, and a negative electrode is particularly preferable to the non-aqueous electrolyte. . This is because a higher effect can be obtained.

  A specific embodiment of the present invention will be described with reference to FIG. However, the present invention is not limited only to these examples.

<Example 1-1>
As the non-aqueous electrolyte secondary battery of Example 1-1, the coin-type secondary battery shown in FIG. 1 was produced. In this secondary battery, a positive electrode 2 and a negative electrode 4 are laminated via a separator 3 made of a microporous polypropylene film impregnated with an electrolytic solution, and sandwiched between an outer can 6 and an outer cup 5, and a gasket 7. It is caulked through.

First, after mixing 94 parts by mass of lithium cobalt composite oxide (LiCoO ₂ ) as a positive electrode active material, 3 parts by mass of graphite as a conductive agent, and 3 parts by mass of polyvinylidene fluoride as a binder, N-methyl-2 -Pyrrolidone was added to obtain a positive electrode mixture slurry.

  Next, the obtained positive electrode mixture slurry was uniformly applied to a positive electrode current collector 2A made of an aluminum foil having a thickness of 20 μm and dried to form a positive electrode active material layer 2B having a thickness of 70 μm. After that, the positive electrode current collector 2A on which the positive electrode active material layer 2B was formed was punched into a circle having a diameter of 15 mm, and thus the positive electrode 2 was obtained.

  Further, using graphite as a negative electrode active material, 97 parts by mass of this graphite and 3 parts by mass of polyvinylidene fluoride as a binder are added, N-methyl-2-pyrrolidone is added, and a copper foil having a thickness of 15 μm is used. A negative electrode active material layer 4B having a thickness of 70 μm was formed by uniformly coating and drying the negative electrode current collector 4A. After that, the negative electrode current collector 4A on which the negative electrode active material layer 4B was formed was punched into a circle having a diameter of 16 mm, whereby the negative electrode 4 was obtained.

Next, after laminating the positive electrode 2 and the negative electrode 4 via a separator 3 made of a microporous polypropylene film having a thickness of 25 μm, an electrolytic solution is injected into the separator 3, and these are attached to the stainless steel outer cup 5. The secondary battery of Example 1-1 was obtained by putting it in the outer can 6 and caulking them. As an electrolytic solution, LiPF ₆ was added at 1.0 mol / kg as an electrolyte salt in a solvent in which ethylene carbonate (EC) and diethyl carbonate (DEC) were mixed at a composition of a weight ratio (EC: DEC) of 3: 7. The compound represented by formula (15) was added so that the concentration was 0.5 wt%.

<Example 1-2>
A secondary battery of Example 1-2 was made in the same manner as Example 1-1 except that the amount of the compound represented by Formula (15) was changed to 3 wt%.

<Example 1-3>
Instead of adding the compound represented by formula (15), the same procedure as in Example 1-1 was performed except that 0.5 wt% of the compound represented by formula (16) was added. A secondary battery was produced.

<Example 1-4>
Instead of adding the compound represented by formula (15), the secondary of Example 1-4 was obtained in the same manner as in Example 1-1 except that 3 wt% of the compound represented by formula (16) was added. A battery was produced.

<Example 1-5>
Instead of adding the compound represented by formula (15), the same procedure as in Example 1-1 was performed except that 0.5 wt% of the compound represented by formula (17) was added. A secondary battery was produced.

<Example 1-6>
Instead of adding the compound represented by formula (15), the secondary of Example 1-6 was obtained in the same manner as in Example 1-1 except that 3 wt% of the compound represented by formula (17) was added. A battery was produced.

<Example 1-7>
Instead of adding the compound represented by the formula (15), the same procedure as in Example 1-1 was performed except that 0.5 wt% of the compound represented by the formula (18) was added. A secondary battery was produced.

<Example 1-8>
Instead of adding the compound represented by formula (15), the secondary of Example 1-8 was obtained in the same manner as in Example 1-1 except that 3 wt% of the compound represented by formula (18) was added. A battery was produced.

<Example 1-9>
Instead of adding the compound represented by the formula (15), the same procedure as in Example 1-1 was performed except that 0.5 wt% of the compound represented by the formula (19) was added. A secondary battery was produced.

<Example 1-10>
Instead of adding the compound represented by formula (15), the secondary of Example 1-10 was obtained in the same manner as in Example 1-1 except that 3 wt% of the compound represented by formula (19) was added. A battery was produced.

<Example 1-11>
Instead of adding the compound represented by formula (15), the same procedure as in Example 1-1 was performed except that 0.5 wt% of the compound represented by formula (20) was added. A secondary battery was produced.

<Example 1-12>
Instead of adding the compound represented by formula (15), the secondary of Example 1-12 was obtained in the same manner as in Example 1-1 except that 3 wt% of the compound represented by formula (20) was added. A battery was produced.

<Example 1-13>
Instead of adding the compound represented by formula (15), the same procedure as in Example 1-1 was performed except that 0.5 wt% of the compound represented by formula (21) was added. A secondary battery was produced.

<Example 1-14>
Instead of adding the compound represented by formula (15), the secondary of Example 1-14 was obtained in the same manner as in Example 1-1 except that 3 wt% of the compound represented by formula (21) was added. A battery was produced.

<Example 1-15>
Instead of adding the compound represented by formula (15), the same procedure as in Example 1-1 was performed except that 0.5 wt% of the compound represented by formula (22) was added. A secondary battery was produced.

<Example 1-16>
Instead of adding the compound represented by formula (15), the secondary of Example 1-16 was obtained in the same manner as in Example 1-1 except that 3 wt% of the compound represented by formula (22) was added. A battery was produced.

<Example 1-17>
Instead of adding the compound represented by the formula (15), the same procedure as in Example 1-1 was performed except that 0.5 wt% of the compound represented by the formula (23) was added. A secondary battery was produced.

<Example 1-18>
Instead of adding the compound represented by formula (15), the secondary of Example 1-18 was obtained in the same manner as in Example 1-1 except that 3 wt% of the compound represented by formula (23) was added. A battery was produced.

<Comparative Example 1-1>
A secondary battery of Comparative Example 1-1 was produced in the same manner as Example 1-1 except that the compound represented by Formula (15) was not added.

<Comparative Example 1-2>
The secondary battery of Comparative Example 1-2 was performed in the same manner as Example 1-1 except that 0.5 wt% of γ-butyrolactone (GBL) was added instead of adding the compound represented by Formula (15). Was made.

<Example 2-1>
Further, a secondary battery of Example 2-1 was produced in the same manner as Example 1-9, except that 1 wt% of vinylene carbonate (VC) was added as an additive.

<Example 2-2>
Further, the secondary battery of Example 2-2 was made in the same manner as Example 1-9 except that 1 wt% of 4-fluoro-1,3-dioxolan-2-one (FEC) was added as an additive. Was made.

<Example 2-3>
Further, a secondary battery of Example 2-3 was fabricated in the same manner as Example 1-9, except that 1 wt% of succinic anhydride was added as an additive.

<Example 2-4>
Further, a secondary battery of Example 2-4 was fabricated in the same manner as Example 1-9, except that 1 wt% of 2-sulfobenzoic anhydride was added as an additive.

<Example 2-5>
Further, a secondary battery of Example 2-5 was produced in the same manner as Example 1-9 except that 1 wt% of propene sultone was added as an additive.

<Comparative Example 2-1>
A secondary battery of Comparative Example 2-1 was prepared in the same manner as in Example 2-1, except that 0.5 wt% of γ-butyrolactone (GBL) was added instead of the compound represented by Formula (19). Produced.

<Comparative Example 2-2>
A secondary battery of Comparative Example 2-2 was manufactured in the same manner as Example 2-2 except that 0.5 wt% of γ-butyrolactone (GBL) was added instead of the compound represented by formula (19). Produced.

<Comparative Example 2-3>
A secondary battery of Comparative Example 2-3 was manufactured in the same manner as Example 2-3 except that 0.5 wt% of γ-butyrolactone (GBL) was added instead of the compound represented by Formula (19). Produced.

<Comparative Example 2-4>
A secondary battery of Comparative Example 2-4 was manufactured in the same manner as Example 2-4 except that 0.5 wt% of γ-butyrolactone (GBL) was added instead of the compound represented by Formula (19). Produced.

<Comparative Example 2-5>
A secondary battery of Comparative Example 2-5 was obtained in the same manner as Example 2-5 except that 0.5 wt% of γ-butyrolactone (GBL) was added instead of the compound represented by formula (19). Produced.

<Example 3-1>
The secondary salt of Example 3-1 was the same as Example 1-9 except that LIPF ₆ was dissolved to 0.9 mol / kg and LiBF ₄ to 0.1 mol / kg as the electrolyte salt. A battery was produced.

<Example 3-2>
Example 1 was carried out in the same manner as Example 1-9 except that LIPF ₆ was dissolved as 0.9 mol / kg and LiBOB (lithium bisoxalate borate) as 0.1 mol / kg as the electrolyte salt. A secondary battery of 3-2 was produced.

<Example 3-3>
Except that LIPF ₆ was dissolved at 0.9 mol / kg and LiTFSI (bis (trifluoromethanesulfonyl) imide lithium) was dissolved at 0.1 mol / kg as an electrolyte salt, the same as in Example 1-9 A secondary battery of Example 3-3 was produced.

<Example 3-4>
Except that the electrolyte salt was dissolved so that LIPF ₆ was 0.9 mol / kg and 1,3-perfluoropropanedisulfonylimide lithium represented by the formula (49) was 0.1 mol / kg. A secondary battery of Example 3-4 was made in the same manner as Example 1-9.

<Example 4-1>
A secondary battery of Example 4-1 was produced in the same manner as Example 1-1 except that the negative electrode 4 produced as described below was used. A negative electrode active material layer 4B made of silicon (Si) having a thickness of 5 μm was formed on the negative electrode current collector 4A made of a copper foil having a thickness of 15 μm by an evaporation method. After that, the negative electrode current collector 4A on which the negative electrode active material layer 4B was formed was punched into a circle having a diameter of 16 mm, whereby the negative electrode 4 was obtained.

<Example 4-2>
Instead of adding the compound represented by formula (15), the same procedure as in Example 4-2 was performed except that 0.5 wt% of the compound represented by formula (16) was added. A secondary battery was produced.

<Example 4-3>
Instead of adding the compound represented by the formula (15), the same procedure as in Example 4-1 was performed except that 0.5 wt% of the compound represented by the formula (17) was added. A secondary battery was produced.

<Example 4-4>
Instead of adding the compound represented by the formula (15), the same procedure as in Example 4-1 was conducted except that 0.5 wt% of the compound represented by the formula (18) was added. A secondary battery was produced.

<Example 4-5>
Instead of adding the compound represented by the formula (15), the same procedure as in Example 4-1 was conducted except that 0.5 wt% of the compound represented by the formula (19) was added. A secondary battery was produced.

<Example 4-6>
Instead of adding the compound represented by the formula (15), the same procedure as in Example 4-1 was performed except that 0.5 wt% of the compound represented by the formula (20) was added. A secondary battery was produced.

<Example 4-7>
Instead of adding the compound represented by the formula (15), the same procedure as in Example 4-1 was conducted except that 0.5 wt% of the compound represented by the formula (21) was added. A secondary battery was produced.

<Example 4-8>
Instead of adding the compound represented by the formula (15), the same procedure as in Example 4-1 was performed except that 0.5 wt% of the compound represented by the formula (22) was added. A secondary battery was produced.

<Example 4-9>
Instead of adding the compound represented by the formula (15), the same procedure as in Example 4-1 was conducted except that 0.5 wt% of the compound represented by the formula (23) was added. A secondary battery was produced.

<Example 4-10>
As an electrolytic solution, as an electrolyte salt, a solvent in which 4-fluoro-1,3-dioxolan-2-one (FEC) and diethyl carbonate (DEC) are mixed at a weight ratio (FEC: DEC) 1: 1 composition, The same as Example 4-1 except that LiPF ₆ was dissolved to 1.0 mol / kg and the compound represented by the formula (15) was added to 0.5 wt%. Thus, a secondary battery of Example 4-10 was produced.

<Example 4-11>
A secondary battery of Example 4-11 was made in the same manner as Example 4-10 except that the amount of the compound represented by formula (15) was changed to 3 wt%.

<Example 4-12>
Instead of the compound represented by the formula (15), a compound represented by the formula (16) was added in the same manner as in Example 4-10 except that 0.5 wt% of the compound represented by the formula (16) was added. A secondary battery was produced.

<Example 4-13>
The secondary battery of Example 4-13 is similar to Example 4-10 except that 3 wt% of the compound represented by formula (16) is added instead of the compound represented by formula (15). Was made.

<Example 4-14>
Instead of the compound represented by the formula (15), a compound represented by the formula (17) was added in the same manner as in Example 4-10 except that 0.5 wt% of the compound represented by the formula (17) was added. A secondary battery was produced.

<Example 4-15>
The secondary battery of Example 4-15 is similar to Example 4-10 except that 3 wt% of the compound represented by formula (17) is added instead of the compound represented by formula (15). Was made.

<Example 4-16>
Instead of the compound represented by the formula (15), a compound represented by the formula (18) was added in the same manner as in Example 4-10 except that 0.5 wt% of the compound represented by the formula (18) was added. A secondary battery was produced.

<Example 4-17>
The secondary battery of Example 4-17 is similar to Example 4-10 except that 3 wt% of the compound represented by formula (18) is added instead of the compound represented by formula (15). Was made.

<Example 4-18>
Instead of the compound represented by the formula (15), a compound represented by the formula (19) was added in the same manner as in Example 4-10 except that 0.5 wt% of the compound represented by the formula (19) was added. A secondary battery was produced.

<Example 4-19>
The secondary battery of Example 4-19 is similar to Example 4-10 except that 3 wt% of the compound represented by formula (19) is added instead of the compound represented by formula (15). Was made.

<Example 4-20>
Instead of the compound represented by formula (15), the compound represented by formula (20) was added in the same manner as in Example 4-10 except that 0.5 wt% of the compound represented by formula (20) was added. A secondary battery was produced.

<Example 4-21>
The secondary battery of Example 4-21 is similar to Example 4-10 except that 3 wt% of the compound represented by formula (20) is added instead of the compound represented by formula (15). Was made.

<Example 4-22>
Instead of the compound represented by formula (15), the compound represented by formula (21) was added in the same manner as in Example 4-10 except that 0.5 wt% of the compound represented by formula (21) was added. A secondary battery was produced.

<Example 4-23>
The secondary battery of Example 4-23 is similar to Example 4-10 except that 3 wt% of the compound represented by formula (21) is added instead of the compound represented by formula (15). Was made.

<Example 4-24>
Instead of the compound represented by formula (15), the compound represented by formula (22) was added in the same manner as in Example 4-10 except that 0.5 wt% of the compound represented by formula (22) was added. A secondary battery was produced.

<Example 4-25>
The secondary battery of Example 4-25 is similar to Example 4-10 except that 3 wt% of the compound represented by formula (22) is added instead of the compound represented by formula (15). Was made.

<Example 4-26>
Instead of the compound represented by the formula (15), a compound represented by the formula (23) was added in the same manner as in Example 4-10 except that 0.5 wt% of the compound represented by the formula (23) was added. A secondary battery was produced.

<Example 4-27>
The secondary battery of Example 4-27 is similar to Example 4-10 except that 3 wt% of the compound represented by formula (23) is added instead of the compound represented by formula (15). Was made.

<Example 4-28>
As an electrolytic solution, propylene carbonate (PC), 4,5-difluoro-1,3-dioxolan-2-one (DFEC) and diethyl carbonate (DEC) in a weight ratio (PC: DFEC: DEC) 4: 1: 5. In the solvent mixed in the composition, LiPF ₆ was dissolved as an electrolyte salt so as to be 1.0 mol / kg, and the compound represented by the formula (15) was added so as to be 0.5 wt%. A secondary battery of Example 4-28 was produced in the same manner as Example 4-1, except for the above.

<Example 4-29>
Instead of the compound represented by formula (15), the secondary of Example 4-29 was obtained in the same manner as in Example 4-28 except that 0.5 wt of the compound represented by formula (16) was added. A battery was produced.

<Example 4-30>
Instead of the compound represented by formula (15), the secondary of Example 4-30 was obtained in the same manner as in Example 4-28 except that 0.5 wt of the compound represented by formula (17) was added. A battery was produced.

<Example 4-31>
Instead of the compound represented by formula (15), the secondary of Example 4-31 was obtained in the same manner as in Example 4-28 except that 0.5 wt of the compound represented by formula (18) was added. A battery was produced.

<Example 4-32>
Instead of the compound represented by formula (15), the secondary of Example 4-32 was obtained in the same manner as in Example 4-28 except that 0.5 wt of the compound represented by formula (19) was added. A battery was produced.

<Example 4-33>
Instead of the compound represented by formula (15), the secondary of Example 4-33 was obtained in the same manner as in Example 4-28 except that 0.5 wt of the compound represented by formula (20) was added. A battery was produced.

<Example 4-34>
Instead of the compound represented by formula (15), the secondary of Example 4-34 was obtained in the same manner as in Example 4-28 except that 0.5 wt of the compound represented by formula (21) was added. A battery was produced.

<Example 4-35>
Instead of the compound represented by formula (15), the secondary of Example 4-35 was obtained in the same manner as in Example 4-28 except that 0.5 wt of the compound represented by formula (22) was added. A battery was produced.

<Example 4-36>
Instead of the compound represented by formula (15), the secondary of Example 4-36 was obtained in the same manner as in Example 4-28 except that 0.5 wt of the compound represented by formula (23) was added. A battery was produced.

<Comparative Example 4-1>
A secondary battery of Comparative Example 4-1 was produced in the same manner as in Example 4-1, except that the compound represented by formula (15) was not added.

<Comparative Example 4-2>
A secondary battery of Comparative Example 4-2 was produced in the same manner as Example 4-1, except that γ-butyrolactone (GBL) was added instead of adding the compound represented by Formula (15).

<Comparative Example 4-3>
A secondary battery of Comparative Example 4-3 was made in the same manner as Example 4-10, except that the compound represented by formula (15) was not added.

<Comparative Example 4-4>
A secondary battery of Comparative Example 4-4 was made in the same manner as Example 4-10 except that γ-butyrolactone (GBL) was added instead of adding the compound represented by Formula (15).

<Comparative Example 4-5>
A secondary battery of Comparative Example 4-5 was made in the same manner as Example 4-28, except that the compound represented by formula (15) was not added.

<Comparative Example 4-6>
A secondary battery of Comparative Example 4-6 was made in the same manner as Example 4-28, except that γ-butyrolactone (GBL) was added instead of adding the compound represented by formula (15).

<Example 5-1>
Further, a secondary battery of Example 5-1 was produced in the same manner as Example 4-18 except that 1 wt% of vinylene carbonate (VC) was added as an additive.

<Example 5-2>
Further, a secondary battery of Example 5-2 was made in the same manner as Example 4-18 except that 1 wt% of succinic anhydride was added as an additive.

<Example 5-3>
Further, a secondary battery of Example 5-3 was produced in the same manner as Example 4-18, except that 1 wt% of 2-sulfobenzoic anhydride was added as an additive.

<Example 5-4>
Further, a secondary battery of Example 5-4 was produced in the same manner as Example 4-18, except that 1 wt% of propene sultone was added as an additive.

<Example 6-1>
The secondary salt of Example 6-1 was the same as Example 4-18 except that LIPF ₆ was dissolved to 0.9 mol / kg and LiBF ₄ to 0.1 mol / kg as the electrolyte salt. A battery was produced.

<Example 6-2>
Example 4 was carried out in the same manner as Example 4-18 except that LIPF ₆ was dissolved as an electrolyte salt at 0.9 mol / kg and lithium bisoxalate borate (LiBOB) was dissolved at 0.1 mol / kg. A secondary battery of 6-2 was produced.

<Example 6-3>
Except that LIPF ₆ was dissolved at 0.9 mol / kg and bis (trifluoromethanesulfonyl) imidolithium (LiTFSI) was dissolved at 0.1 mol / kg as an electrolyte salt, the same as in Example 4-18. A secondary battery of Example 6-3 was produced.

<Example 6-4>
Except that the electrolyte salt was dissolved so that LIPF ₆ was 0.9 mol / kg and 1,3-perfluoropropanedisulfonylimide lithium represented by the formula (49) was 0.1 mol / kg. A secondary battery of Example 6-4 was made in the same manner as Example 4-18.

<Example 7-1>
A secondary battery of Example 7-1 was produced in the same manner as Example 1-1 except that the negative electrode 4 was produced as described below. When producing the negative electrode 4, first, a tin / cobalt / indium / titanium alloy powder and a carbon powder were mixed, and then a CoSnC-containing material was synthesized using a mechanochemical reaction. When the composition of this CoSnC-containing material was analyzed, the tin content was 48% by mass, the cobalt content was 23% by mass, the carbon content was 20% by mass, and the ratio of cobalt to the total of tin and cobalt Co / (Sn + Co) was 32 mass%.

  Next, 80 parts by mass of the above-mentioned CoSnC-containing material powder as a negative electrode active material, 12 parts by mass of graphite as a conductive agent, and 8 parts by mass of polyvinylidene fluoride as a binder are mixed, and N-methyl- which is a solvent is mixed. Dispersed in 2-pyrrolidone. Finally, the negative electrode active material layer 4B was formed by applying and drying the negative electrode current collector 4A made of copper foil (15 μm thick), followed by compression molding. Next, the negative electrode current collector 4A on which the negative electrode active material layer 4B was formed was punched into a circle having a diameter of 16 mm, whereby the negative electrode 4 was obtained.

<Example 7-2>
A secondary battery of Example 7-2 was produced in the same manner as Example 7-1 except that the amount of the compound represented by Formula (15) was changed to 3 wt%.

<Example 7-3>
Instead of the compound represented by formula (15), the same procedure as in Example 7-1 was performed except that 0.5 wt% of the compound represented by formula (16) was added. A secondary battery was produced.

<Example 7-4>
A secondary battery of Example 7-4 was obtained in the same manner as Example 7-1 except that 3 wt% of the compound represented by formula (16) was added instead of the compound represented by formula (15). Was made.

<Example 7-5>
Instead of the compound represented by formula (15), the same procedure as in Example 7-1 was conducted except that 0.5 wt% of the compound represented by formula (17) was added. A secondary battery was produced.

<Example 7-6>
A secondary battery of Example 7-6 was obtained in the same manner as Example 7-1 except that 3 wt% of the compound represented by formula (17) was added instead of the compound represented by formula (15). Was made.

<Example 7-7>
Instead of the compound represented by formula (15), the same procedure as in Example 7-1 was conducted except that 0.5 wt% of the compound represented by formula (18) was added. A secondary battery was produced.

<Example 7-8>
A secondary battery of Example 7-8 was obtained in the same manner as Example 7-1 except that 3 wt% of the compound represented by formula (18) was added instead of the compound represented by formula (15). Was made.

<Example 7-9>
Instead of the compound represented by formula (15), the same procedure as in Example 7-1 was conducted except that 0.5 wt% of the compound represented by formula (19) was added. A secondary battery was produced.

<Example 7-10>
A secondary battery of Example 7-10 was obtained in the same manner as Example 7-1 except that 3 wt% of the compound represented by formula (19) was added instead of the compound represented by formula (15). Was made.

<Example 7-11>
Instead of the compound represented by formula (15), the same procedure as in Example 7-1 was conducted except that 0.5 wt% of the compound represented by formula (20) was added. A secondary battery was produced.

<Example 7-12>
A secondary battery of Example 7-12 was obtained in the same manner as Example 7-1 except that 3 wt% of the compound represented by formula (20) was added instead of the compound represented by formula (15). Was made.

<Example 7-13>
Instead of the compound represented by formula (15), the same procedure as in Example 7-1 was conducted except that 0.5 wt% of the compound represented by formula (21) was added. A secondary battery was produced.

<Example 7-14>
The secondary battery of Example 7-14 is similar to Example 7-1 except that 3 wt% of the compound represented by formula (21) is added instead of the compound represented by formula (15). Was made.

<Example 7-15>
Instead of the compound represented by formula (15), the same procedure as in Example 7-1 was conducted except that 0.5 wt% of the compound represented by formula (22) was added. A secondary battery was produced.

<Example 7-16>
A secondary battery of Example 7-16 was obtained in the same manner as Example 7-1 except that 3 wt% of the compound represented by formula (22) was added instead of the compound represented by formula (15). Was made.

<Example 7-17>
Instead of the compound represented by formula (15), the same procedure as in Example 7-1 was conducted except that 0.5 wt% of the compound represented by formula (23) was added. A secondary battery was produced.

<Example 7-18>
A secondary battery of Example 7-18 was obtained in the same manner as Example 7-1 except that 3 wt% of the compound represented by formula (23) was added instead of the compound represented by formula (15). Was made.

<Comparative Example 7-1>
A secondary battery of Comparative Example 7-1 was produced in the same manner as Example 7-1 except that the compound represented by formula (15) was not added.

<Comparative Example 7-2>
A secondary battery of Comparative Example 7-2 was produced in the same manner as Example 7-1 except that γ-butyrolactone (GBL) was added instead of the compound represented by Formula (15).

<Example 8-1>
Instead of the negative electrode 4, the negative electrode 100 shown in FIG. 6 was prepared and used as described below, and Example 1 except that the compound represented by formula (15) was not added to the electrolytic solution. In the same manner as in Example 1, a secondary battery of Example 8-1 was produced. When producing the negative electrode 100, first, graphite is used as a negative electrode active material, 97 parts by mass of this graphite and 3 parts by mass of polyvinylidene fluoride as a binder are mixed, and N-methyl-2-pyrrolidone is added. Then, a negative electrode active material layer 102 having a thickness of 60 μm was formed by uniformly applying and drying the negative electrode current collector 101 made of a copper foil having a thickness of 15 μm. Next, a 3 wt% aqueous solution in which the compound represented by the formula (19) was dissolved was prepared. After that, the negative electrode current collector 101 (4A) on which the negative electrode active material layer 102 (4B) is formed is dipped in an aqueous solution for several seconds and then pulled up, and then dried in a reduced pressure environment at 60 ° C. to obtain a negative electrode active material. A film 103 was formed over the material layer 102 (4B). Finally, the negative electrode current collector 101 (4A) on which the negative electrode active material layer 102 (4B) and the film 103 were formed was punched into a circle having a diameter of 16 mm, thereby obtaining the negative electrode 100 (4).

<Example 8-2>
A secondary battery of Example 8-2 was produced in the same manner as Example 8-1 except that the compound represented by formula (20) was used instead of the compound represented by formula (19). did.

<Example 8-3>
A secondary battery of Example 8-3 was produced in the same manner as Example 8-1 except that the compound represented by formula (21) was used instead of the compound represented by formula (19). did.

<Example 8-4>
A secondary battery of Example 8-4 was produced in the same manner as Example 8-1 except that the compound represented by formula (22) was used instead of the compound represented by formula (19). did.

<Example 8-5>
A secondary battery of Example 8-5 was produced in the same manner as Example 8-1 except that the compound represented by formula (24) was used instead of the compound represented by formula (19). did.

<Example 9-1>
A secondary battery of Example 9-1 was produced in the same manner as in Example 8-1, except that the negative electrode 100 (4) produced as described below was used. When producing the negative electrode 100 (4), first, the negative electrode active material layer 102 made of silicon (Si) having a thickness of 5 μm is formed on one surface of the negative electrode current collector 101 made of copper foil having a thickness of 15 μm by vapor deposition. did. Next, a 3 wt% aqueous solution in which the compound represented by the formula (19) was dissolved was prepared. Next, the negative electrode current collector 101 (4A) on which the negative electrode active material layer 102 (4B) is formed is dipped in an aqueous solution for several seconds and then pulled up, and then dried in a reduced pressure environment at 60 ° C. to obtain a negative electrode active material. A film 103 was formed over the material layer 102 (4B). Finally, the negative electrode current collector 101 (4A) on which the negative electrode active material layer 102 (4B) and the film 103 were formed was punched into a circle having a diameter of 16 mm, thereby obtaining the negative electrode 100 (4).

<Example 9-2>
A secondary battery of Example 9-2 was produced in the same manner as Example 9-1 except that the compound represented by formula (20) was used instead of the compound represented by formula (19). did.

<Example 9-3>
A secondary battery of Example 9-3 was produced in the same manner as Example 9-1 except that the compound represented by formula (21) was used instead of the compound represented by formula (19). did.

<Example 9-4>
A secondary battery of Example 9-4 was produced in the same manner as Example 9-1 except that the compound represented by formula (22) was used instead of the compound represented by formula (19). did.

<Example 9-5>
A secondary battery of Example 9-5 was produced in the same manner as Example 9-1 except that the compound represented by formula (24) was used instead of the compound represented by formula (19). did.

<Example 9-6>
As an electrolytic solution, as an electrolyte salt, a solvent in which 4-fluoro-1,3-dioxolan-2-one (FEC) and diethyl carbonate (DEC) are mixed at a weight ratio (FEC: DEC) 1: 1 composition, A secondary battery of Example 9-6 was produced in the same manner as Example 9-1 except that LiPF ₆ dissolved at 1.0 mol / kg was used.

<Example 9-7>
A secondary battery of Example 9-7 was produced in the same manner as Example 9-6 except that the compound represented by formula (20) was used instead of the compound represented by formula (19). did.

<Example 9-8>
A secondary battery of Example 9-8 was produced in the same manner as Example 9-6 except that the compound represented by formula (21) was used instead of the compound represented by formula (19). did.

<Example 9-9>
A secondary battery of Example 9-9 was produced in the same manner as Example 9-6 except that the compound represented by formula (22) was used instead of the compound represented by formula (19). did.

<Example 9-10>
A secondary battery of Example 9-10 was produced in the same manner as Example 9-6 except that the compound represented by formula (24) was used instead of the compound represented by formula (19). did.

<Example 9-11>
As an electrolytic solution, propylene carbonate (PC), 4,5-difluoro-1,3-dioxolan-2-one (DFEC) and diethyl carbonate (DEC) in a weight ratio (PC: DFEC: DEC) 4: 1: 5. Example 9-11 was performed in the same manner as Example 9-1 except that LiPF ₆ dissolved in 1.0 mol / kg as an electrolyte salt was used in the solvent mixed with the composition of A secondary battery was prepared.

<Example 9-12>
A secondary battery of Example 9-12 was produced in the same manner as Example 9-11 except that the compound represented by formula (20) was used instead of the compound represented by formula (19). did.

<Example 9-13>
A secondary battery of Example 9-13 was produced in the same manner as Example 9-11 except that the compound represented by formula (21) was used instead of the compound represented by formula (19). did.

<Example 9-14>
A secondary battery of Example 9-14 was produced in the same manner as Example 9-11 except that the compound represented by formula (22) was used instead of the compound represented by formula (19). did.

<Example 9-15>
A secondary battery of Example 9-15 was produced in the same manner as Example 9-11 except that the compound represented by formula (24) was used instead of the compound represented by formula (19). did.

<Example 10-1>
A secondary battery of Example 10-1 was produced in the same manner as Example 9-7, except that 1 wt% of vinylene carbonate (VC) was further added as an additive to the electrolytic solution.

<Example 10-2>
A secondary battery of Example 10-2 was produced in the same manner as Example 9-7, except that 1 wt% of succinic anhydride was further added as an additive to the electrolytic solution.

<Example 10-3>
A secondary battery of Example 10-3 was produced in the same manner as Example 9-7, except that 1 wt% of 2-sulfobenzoic anhydride was further added as an additive to the electrolytic solution.

<Example 10-4>
A secondary battery of Example 10-4 was made in the same manner as Example 9-7, except that 1 wt% of propene sultone was further added as an additive to the electrolytic solution.

<Example 11-1>
The secondary salt of Example 11-1 was the same as Example 9-7 except that LIPF ₆ was dissolved to 0.9 mol / kg and LiBF ₄ to 0.1 mol / kg as the electrolyte salt. A battery was produced.

<Example 11-2>
Example 9-7 was carried out in the same manner as Example 9-7 except that LIPF ₆ was dissolved at 0.9 mol / kg and lithium bisoxalate borate (LiBOB) was dissolved at 0.1 mol / kg as the electrolyte salt. A secondary battery of 11-2 was produced.

<Example 11-3>
Except that LIPF ₆ was dissolved at 0.9 mol / kg and bis (trifluoromethanesulfonyl) imidolithium (LiTFSI) was dissolved at 0.1 mol / kg as an electrolyte salt, the same as in Example 9-7. A secondary battery of Example 11-3 was produced.

<Example 11-4>
Except that the electrolyte salt was dissolved so that LIPF ₆ was 0.9 mol / kg and 1,3-perfluoropropanedisulfonylimide lithium represented by the formula (49) was 0.1 mol / kg. A secondary battery of Example 11-4 was produced in the same manner as Example 9-7.

<Example 12-1>
A secondary battery of Example 12-1 was produced in the same manner as Example 9-7, except that the negative electrode 100 (4) produced as described below was used. A plurality of negative electrode active material particles made of silicon (Si) having a thickness of 5 μm were formed on a negative electrode current collector 101 (4A) made of a copper foil having a thickness of 15 μm by a vapor deposition method. Thereafter, a negative electrode active material layer 102 was formed by depositing silicon oxide (SiO ₂ ) as an oxide-containing film on the surface of the negative electrode active material particles by a liquid phase deposition method. When forming the oxide-containing film, the negative electrode current collector 101 (4A) on which the negative electrode active material particles were formed was immersed in a solution in which boron as an anion scavenger was dissolved in hydrofluoric acid for 3 hours. After depositing a silicon oxide on the surface of the negative electrode active material particles, it was washed with water and dried under reduced pressure. Next, a 3 wt% aqueous solution in which the compound represented by the formula (20) was dissolved was prepared. Next, the negative electrode current collector 101 (4A) on which the negative electrode active material layer 102 (4B) is formed is dipped in an aqueous solution for several seconds and then pulled up, and then dried in a reduced pressure environment at 60 ° C. to obtain a negative electrode active material. A film 103 was formed over the material layer 102 (4B). Finally, the negative electrode current collector 101 (4A) on which the negative electrode active material layer 102 (4B) and the film 103 were formed was punched into a circle having a diameter of 16 mm, thereby obtaining the negative electrode 100 (4).

<Example 12-2>
A secondary battery of Example 12-2 was produced in the same manner as Example 9-7, except that the negative electrode 100 (4) produced as described below was used. A plurality of negative electrode active material particles made of silicon (Si) having a thickness of 5 μm were formed on a negative electrode current collector 101 (4A) made of a copper foil having a thickness of 15 μm by a vapor deposition method. Next, a negative electrode active material layer 102 was formed by growing a cobalt (Co) plating film as a metal material by an electrolytic plating method. When forming the metal material, electricity was supplied while supplying air to the plating bath, and cobalt was deposited on one surface of the negative electrode current collector 101 (4A). At this time, a cobalt plating solution manufactured by Japan High Purity Chemical Co., Ltd. was used as the plating solution, the current density was 2 A / dm ^{2 to} 5 A / dm ² , and the plating rate was 10 nm / second. Next, a 3 wt% aqueous solution in which the compound represented by the formula (20) was dissolved was prepared. Next, the negative electrode current collector 101 (4A) on which the negative electrode active material layer 102 (4B) is formed is dipped in an aqueous solution for several seconds and then pulled up, and then dried in a reduced pressure environment at 60 ° C. to obtain a negative electrode active material. A film 103 was formed over the material layer 102 (4B). Finally, the negative electrode current collector 101 (4A) on which the negative electrode active material layer 102 (4B) and the film 103 were formed was punched into a circle having a diameter of 16 mm, thereby obtaining the negative electrode 100 (4).

<Example 12-3>
A secondary battery of Example 12-3 was produced in the same manner as Example 9-7, except that the negative electrode 100 (4) produced as described below was used. A plurality of negative electrode active material particles made of silicon (Si) having a thickness of 5 μm were formed on a negative electrode current collector 101 (4A) made of a copper foil having a thickness of 15 μm by a vapor deposition method. Next, in the same manner as in Example 12-1, a silicon oxide (SiO ₂ ) was deposited as an oxide-containing film on the surface of the negative electrode active material particles by a liquid phase deposition method. After that, in the same manner as in Example 12-2, a negative electrode active material layer 102 was formed by growing a plating film of cobalt (Co) as a metal material by an electrolytic plating method. Next, a 3 wt% aqueous solution in which the compound represented by the formula (20) was dissolved was prepared. Next, the negative electrode current collector 101 (4A) on which the negative electrode active material layer 102 (4B) is formed is dipped in an aqueous solution for several seconds and then pulled up, and then dried in a reduced pressure environment at 60 ° C. to obtain a negative electrode active material. A film 103 was formed over the material layer 102 (4B). Finally, the negative electrode current collector 101 (4A) on which the negative electrode active material layer 102 (4B) and the film 103 were formed was punched into a circle having a diameter of 16 mm, thereby obtaining the negative electrode 100 (4).

<Comparative Example 12-1>
A secondary battery of Comparative Example 12-1 was produced in the same manner as Example 12-1, except that the film 103 was not formed.

<Comparative Example 12-2>
A secondary battery of Comparative Example 12-2 was produced in the same manner as Example 12-2 except that the film 103 was not formed.

<Comparative Example 12-3>
A secondary battery of Comparative Example 12-3 was produced in the same manner as Example 12-3, except that the film 103 was not formed.

<Example 13-1>
A secondary battery of Example 13-1 was produced in the same manner as Example 9-6 except that the negative electrode 100 was produced as described below. When producing the negative electrode 100, first, silicon powder having an average particle diameter of 1 μm was used as the negative electrode active material, 95 parts by mass of this silicon powder and 5 parts by mass of polyimide as the binder were mixed, and N-methyl- 2-Pyrrolidone was added to the negative electrode current collector 101 made of a copper foil having a thickness of 18 μm, uniformly applied and dried, and then pressed. After that, the negative electrode active material layer 102 having a thickness of 20 μm was formed by heating at 400 ° C. for 12 hours in a vacuum atmosphere. Next, a 3 wt% aqueous solution in which the compound represented by the formula (19) was dissolved was prepared. Next, the negative electrode current collector 101 (4A) on which the negative electrode active material layer 102 (4B) is formed is dipped in an aqueous solution for several seconds and then pulled up, and then dried in a reduced pressure environment at 60 ° C. to obtain a negative electrode active material. A film 103 was formed over the material layer 102 (4B). Finally, the negative electrode current collector 101 (4A) on which the negative electrode active material layer 102 (4B) and the film 103 were formed was punched into a circle having a diameter of 16 mm, thereby obtaining the negative electrode 100 (4).

<Example 13-2>
A secondary battery of Example 13-2 was produced in the same manner as Example 13-1, except that the compound represented by Formula (20) was used instead of the compound represented by Formula (19). did.

<Example 13-3>
A secondary battery of Example 13-3 was produced in the same manner as Example 13-1, except that the compound represented by Formula (21) was used instead of the compound represented by Formula (19). did.

<Example 13-4>
A secondary battery of Example 13-4 was produced in the same manner as Example 13-1, except that the compound represented by Formula (22) was used instead of the compound represented by Formula (19). did.

<Example 13-5>
A secondary battery of Example 13-5 was produced in the same manner as Example 13-1, except that the compound represented by Formula (24) was used instead of the compound represented by Formula (19). did.

<Example 14-1>
A secondary battery of Example 14-1 was produced in the same manner as Example 8-1, except that the negative electrode 100 was produced as described below. When producing the negative electrode 100, first, a CoSnC-containing material was synthesized in the same manner as in Example 7-1. When the composition of this CoSnC-containing material was analyzed, the content of tin, cobalt and carbon, and the ratio of cobalt to the total of tin and cobalt Co / (Sn + Co) were the same as those of the CoSnC-containing material of Example 7-1. It was.

  Next, 80 parts by mass of the above-mentioned CoSnC-containing material powder as a negative electrode active material, 12 parts by mass of graphite as a conductive agent, and 8 parts by mass of polyvinylidene fluoride as a binder are mixed, and N-methyl- which is a solvent is mixed. Dispersed in 2-pyrrolidone. Next, the negative electrode active material layer 102 (4B) was formed by applying and drying the negative electrode current collector 101 (4A) made of copper foil (15 μm thick), followed by drying. Next, a 3 wt% aqueous solution in which the compound represented by the formula (19) was dissolved was prepared. Next, the negative electrode current collector 101 (4A) on which the negative electrode active material layer 102 (4B) is formed is dipped in an aqueous solution for several seconds and then pulled up, and then dried in a reduced pressure environment at 60 ° C. to obtain a negative electrode active material. A film 103 was formed over the material layer 102 (4B). Finally, the negative electrode current collector 101 (4A) on which the negative electrode active material layer 102 (4B) and the film 103 were formed was punched into a circle having a diameter of 16 mm, thereby obtaining the negative electrode 100 (4).

<Example 14-2>
A secondary battery of Example 14-2 was produced in the same manner as Example 14-1, except that the compound represented by Formula (20) was used instead of the compound represented by Formula (19). did.

<Example 14-3>
A secondary battery of Example 14-3 was produced in the same manner as Example 14-1, except that the compound represented by Formula (21) was used instead of the compound represented by Formula (19). did.

<Example 14-4>
A secondary battery of Example 14-4 was produced in the same manner as Example 14-1, except that the compound represented by Formula (22) was used instead of the compound represented by Formula (19). did.

<Example 14-5>
A secondary battery of Example 14-5 was produced in the same manner as Example 14-1, except that the compound represented by Formula (24) was used instead of the compound represented by Formula (19). did.

<Example 15-1>
Instead of the positive electrode 2, the positive electrode 300 shown in FIG. 11 was prepared and used as described below, and Example 7- except that the compound represented by the formula (15) was not added to the electrolytic solution. In the same manner as in Example 1, a secondary battery of Example 15-1 was produced. In forming the positive electrode 300 (2), first, 94 parts by mass of lithium cobalt composite oxide (LiCoO ₂ ) as a positive electrode active material, 3 parts by mass of graphite as a conductive agent, and 3 parts by mass of polyvinylidene fluoride as a binder. After mixing the parts, N-methyl-2-pyrrolidone was added to obtain a positive electrode mixture slurry. Next, the obtained positive electrode mixture slurry was uniformly applied to one surface of a positive electrode current collector 301 (2A) made of an aluminum foil having a thickness of 20 μm and dried to form a positive electrode active material layer 302 (2B). Next, a 3 wt% aqueous solution in which the compound represented by the formula (19) was dissolved was prepared. Next, the positive electrode current collector 301 (2A) on which the positive electrode active material layer 302 (2B) is formed is dipped in an aqueous solution for several seconds and then pulled up, and then dried in a reduced pressure environment at 60 ° C. A film 303 was formed over the material layer 302 (2B). Finally, the positive electrode current collector 301 (2A) on which the positive electrode active material layer 302 (2B) and the coating 303 were formed was punched into a circle having a diameter of 15 mm, thereby obtaining the positive electrode 300 (2).

<Example 15-2>
A secondary battery of Example 15-2 was produced in the same manner as Example 15-1, except that the compound represented by Formula (20) was used instead of the compound represented by Formula (19). did.

<Example 15-3>
A secondary battery of Example 15-3 was produced in the same manner as Example 15-1, except that the compound represented by Formula (21) was used instead of the compound represented by Formula (19). did.

<Example 15-4>
A secondary battery of Example 15-4 was produced in the same manner as Example 15-1, except that the compound represented by Formula (22) was used instead of the compound represented by Formula (19). did.

<Example 15-5>
A secondary battery of Example 15-5 was fabricated in the same manner as Example 15-1, except that the compound represented by formula (24) was used instead of the compound represented by formula (19). did.

<Example 16-1>
Instead of the separator 3, the separator 400 shown in FIG. 12 was prepared and used as described below, and Example 7− was used except that the compound represented by the formula (15) was not added to the electrolytic solution. In the same manner as in Example 1, a secondary battery of Example 16-1 was produced. When forming the separator 400 (3), first, a 3 wt% aqueous solution in which the compound represented by the formula (19) was dissolved was prepared. Next, a microporous membrane 401 made of a microporous polypropylene film having a thickness of 25 μm is dipped in an aqueous solution for several seconds and then lifted, and then dried in a reduced pressure environment at 60 ° C. to form a microporous membrane 401 on the microporous membrane 401. A coating 402 was formed. This obtained separator 400 (3).

<Example 16-2>
A secondary battery of Example 16-2 was produced in the same manner as Example 16-1, except that the compound represented by Formula (20) was used instead of the compound represented by Formula (19). did.

<Example 16-3>
A secondary battery of Example 16-3 was produced in the same manner as Example 16-1, except that the compound represented by Formula (21) was used instead of the compound represented by Formula (19). did.

<Example 16-4>
A secondary battery of Example 16-4 was produced in the same manner as Example 16-1, except that the compound represented by Formula (22) was used instead of the compound represented by Formula (19). did.

<Example 16-5>
A secondary battery of Example 16-5 was produced in the same manner as Example 16-1, except that the compound represented by Formula (24) was used instead of the compound represented by Formula (19). did.

  Next, with respect to the fabricated secondary batteries of Example 1-1 to Example 16-5 and Comparative Example 1-1 to Comparative Example 13-1, the discharge capacity maintenance rate after 100 cycles was determined as described below. Measured and evaluated cycle characteristics.

  First, the discharge capacity of the 2nd cycle was calculated | required by charging / discharging 2 cycles in 23 degreeC atmosphere. Subsequently, the discharge capacity at the 100th cycle was determined by charging and discharging 98 cycles in the same atmosphere. Finally, the discharge capacity retention ratio was calculated by (Equation) discharge capacity retention ratio (%) = (discharge capacity at the 100th cycle / discharge capacity at the second cycle) × 100 (%). As charging / discharging conditions of 1 cycle, after carrying out the constant current constant voltage charge to the upper limit voltage 4.2V with the charging current of 0.2C, the constant current discharge was carried out to the final voltage 2.5V with the discharge current of 0.2C. Here, 0.2 C is a current value at which the theoretical capacity can be discharged (charged) in 5 hours.

  Table 1 shows the discharge capacity retention rates of Example 1-1 to Example 1-18 and Comparative Example 1-1 to Comparative Example 1-2. Table 2 shows the discharge capacity retention rates of Example 1-9, Example 2-1 to Example 2-5, and Comparative Example 2-1 to Comparative Example 2-5. Table 3 shows the discharge capacity retention rates of Example 1-9 and Example 3-1 to Example 3-4. Table 4 shows the discharge capacity retention rates of Example 4-1 to Example 4-36 and Comparative Example 4-1 to Comparative Example 4-6. Table 5 shows the discharge capacity retention rates of Example 4-18 and Example 5-1 to Example 5-4. Table 6 shows the discharge capacity retention rates of Example 4-18 and Example 6-1 to Example 6-4. Table 7 shows the discharge capacity retention rates of Example 7-1 to Example 7-18 and Comparative Example 7-1 to Comparative Example 7-2. Table 8 shows the discharge capacity retention rates of Example 8-1 to Example 8-8 and Comparative Example 1-1. Table 9 shows the discharge capacity retention rates of Example 9-1 to Example 9-15, Comparative Example 4-1, Comparative Example 4-3, and Comparative Example 4-5. Table 10 shows the discharge capacity retention rates of Example 9-7 and Example 10-1 to Example 10-4. Table 11 shows the discharge capacity retention ratios of Example 9-7 and Example 11-1 to Example 11-4. Table 12 shows the discharge capacity retention rates of Example 9-7, Example 12-1 to Example 12-3, and Comparative Example 12-1 to Comparative Example 12-3. Table 13 shows the discharge capacity retention rates of Example 13-1 to Example 13-5 and Comparative Example 13-1. Table 14 shows the discharge capacity retention rates of Example 14-1 to Example 14-5 and Comparative Example 7-1. Table 15 shows the discharge capacity retention rates of Example 15-1 to Example 15-5 and Comparative Example 4-1. Table 16 shows the discharge capacity retention ratios of Example 16-1 to Example 16-5 and Comparative Example 4-1.

  As shown in Table 1, in Example 1-1 to Example 1-18, the discharge capacity retention rate was higher than that of Comparative Example 1-1 and Comparative Example 1-2. That is, when a carbon material is used for the negative electrode, it was found that the cycle characteristics can be improved by including any one of the compounds represented by the formulas (15) to (23) in the electrolytic solution. .

  As shown in Table 2, in Example 2-1 to Example 2-5, the discharge capacity retention rate was higher than that in Example 1-9. That is, in the case of using a carbon material for the negative electrode, the compound represented by the formula (13), vinylene carbonate (VC), 4-fluoro-1,3-dioxolan-2-one (FEC), 4,5-difluoro It was found that cycle characteristics can be further improved by using -1,3-dioxolan-2-one (DFEC), succinic anhydride, 2-sulfobenzoic anhydride or propene sultone (PRS) in combination.

As shown in Table 3, in Example 3-1 to Example 3-4, the discharge capacity retention rate was higher than that in Example 1-9. That is, in the case of using a carbon material for the negative electrode, the compound represented by the formula (19) and LiBF ₄ , lithium bisoxalate borate (LiBOB), bis (trifluoromethanesulfonyl) imide lithium (LiTFSI) or 1 as the electrolyte salt It was found that the cycle characteristics can be further improved by using together with 1,3-perfluoropropanedisulfonylimide lithium.

  As shown in Table 4, in Example 4-1 to Example 4-9, the discharge capacity retention rate was higher than that of Comparative Example 4-1 and Comparative Example 4-2. In Example 4-10 to Example 4-27, the discharge capacity retention rate was higher than that of Comparative Example 4-3 and Comparative Example 4-4. In Example 4-28 to Example 4-36, the discharge capacity retention rate was higher than that of Comparative Example 4-5 and Comparative Example 4-6. That is, in the case where a material containing silicon (Si) as a constituent element is used for the negative electrode, the cycle is achieved by including any one of the compounds represented by the formulas (15) to (23) in the electrolytic solution. It was found that the characteristics can be improved.

  As shown in Table 5, in Example 5-1 to Example 5-4, the discharge capacity retention rate was higher than that in Example 4-18. That is, when a material containing silicon (Si) as a constituent element is used for the negative electrode, the compound represented by the formula (19), succinic anhydride, 2-sulfobenzoic anhydride, or propene sultone (PRS) is used in the electrolytic solution. It was found that the cycle characteristics can be further improved by using together.

As shown in Table 6, in Example 6-1 to Example 6-4, the discharge capacity retention rate was substantially the same as in Example 4-18. That is, in the case where a material containing silicon (Si) as a constituent element is used for the negative electrode, the compound represented by the formula (19), LiBF ₄ , lithium bisoxalate borate (LiBOB), bis (trifluoromethanesulfonyl) as the electrolyte salt It was found that imidolithium (LiTFSI) or 1,3-perfluoropropanedisulfonylimide lithium can be used in combination without deteriorating cycle characteristics.

  As shown in Table 7, in Example 7-1 to Example 7-18, the discharge capacity retention rate was higher than that of Comparative Example 7-1 and Comparative Example 7-2. That is, in the case where a material containing tin (Sn) as a constituent element is used for the negative electrode, the electrolyte solution contains any one of the compounds represented by the formulas (15) to (23). It was found that cycle characteristics can be improved.

  In addition, as shown in Table 1, Table 4, and Table 7, a material containing silicon (Si) as a constituent element in the negative electrode or a material containing tin (Sn) as a constituent element in the negative electrode, compared to the case where a carbon material is used in the negative electrode. There was a tendency for the cycle characteristics to deteriorate more when using. That is, any of the compounds represented by the formulas (15) to (23) when a material containing silicon (Si) as a constituent element is used for the negative electrode or a material containing tin (Sn) as a constituent element is used for the negative electrode It has been found that it is particularly effective to use an electrolytic solution containing.

  In the compound represented by formula (1), a compound where X = amino group, a compound where X = halogen group, a compound where X = −OM and M = alkylsilyl group, M = Even if a compound that is a group 1 element in the long-period periodic table other than hydrogen (H) and lithium (Li) or a compound that is a group 2 element in the M = long-period periodic table is used, the above-described examples and comparative examples There is a tendency to obtain similar results. Therefore, in the compound represented by the formula (1), the electrolyte solution includes a compound where X = amino group, a compound where X = halogen group, X = -OM, and M = alkylsilyl group. By including a compound, a compound that is a group 1 element in the long-period periodic table other than M = hydrogen (H) and lithium (Li), or a compound that is a group 2 element in the long-period periodic table, It can be seen that the cycle characteristics can be improved.

  Moreover, although the example mentioned above demonstrated the case where a non-aqueous electrolyte was used as a non-aqueous electrolyte, it exists in the tendency for the same result to be obtained even if it uses a gel-like non-aqueous electrolyte.

  As shown in Table 8, in Example 8-1 to Example 8-5, the discharge capacity retention rate was higher than that in Comparative Example 1-1. That is, when a carbon material is used for the negative electrode, the coating formed on the surface of the negative electrode active material layer includes any one of the compounds represented by formula (19) to formula (22) and formula (24). It was found that the cycle characteristics can be improved by doing so.

  As shown in Table 9, in Example 9-1 to Example 9-5, the discharge capacity retention rate was higher than that in Comparative Example 4-1. In Example 9-6 to Example 9-10, the discharge capacity retention rate was higher than that of Comparative Example 4-3. In Example 9-11 to Example 9-15, the discharge capacity retention rate was higher than that of Comparative Example 4-5. That is, in the case where silicon (Si; vapor deposition method) is used for the negative electrode, the film formed on the surface of the negative electrode active material layer is selected from the compounds represented by formula (19) to formula (22) and formula (24). It was found that the cycle characteristics can be improved by including any of them.

  As shown in Table 10, in Example 10-1 to Example 10-4, the discharge capacity retention rate was higher than that in Example 9-7. That is, in the case of using silicon (Si; vapor deposition method) for the negative electrode, a film formed on the surface of the negative electrode active material layer and containing the compound represented by the formula (20), succinic anhydride, 2-sulfobenzoic anhydride It has been found that the cycle characteristics can be further improved by using in combination with an electrolyte or an electrolyte containing propene sultone (PRS).

As shown in Table 11, in Example 11-1 to Example 11-4, the discharge capacity retention rate was substantially equivalent as compared with Example 9-7. That is, when silicon (Si; vapor deposition method) is used for the negative electrode, a coating film formed on the surface of the negative electrode active material layer and containing the compound represented by the formula (20), and LiBF ₄ , lithium bisoxalate as the electrolyte salt It was found that high cycle characteristics can be maintained by using in combination with an electrolytic solution containing borate (LiBOB), bis (trifluoromethanesulfonyl) imide lithium (LiTFSI) or 1,3-perfluoropropanedisulfonylimide lithium.

  As shown in Table 12, in Example 12-1, the discharge capacity retention rate was higher than that in Comparative Example 12-1. In Example 12-2, the discharge capacity retention rate was higher than that in Comparative Example 12-2. In Example 12-3, the discharge capacity retention rate was higher than that in Comparative Example 12-3. In Example 12-1 to Example 12-3, the discharge capacity retention rate was higher than that in Example 9-7. That is, in the case of using silicon (Si; vapor deposition method) for the negative electrode, a film formed on the surface of the negative electrode active material layer and containing a compound represented by the formula (20), and an oxide film or the negative electrode active material layer has It was found that the cycle characteristics can be further improved by using a metal material together.

  As shown in Table 13, in Example 13-1 to Example 13-5, the discharge capacity retention rate was higher than that of Comparative Example 13-1. That is, when silicon (Si; sintering method) is used for the negative electrode, the coating formed on the surface of the negative electrode active material layer is composed of the compounds represented by the formulas (19) to (22) and (24). It was found that the cycle characteristics can be improved by including any of them.

  As shown in Table 14, in Example 14-1 to Example 14-5, the discharge capacity retention rate was higher than that of Comparative Example 7-1. That is, in the case where a material containing tin (Sn) as a constituent element is used for the negative electrode, the film formed on the surface of the negative electrode active material layer is a compound represented by formula (19) to formula (22) or formula (24) It was found that the cycle characteristics can be improved by including any of the above.

  Further, as shown in Table 8, Table 9, Table 13, and Table 14, a material containing silicon (Si) as a constituent element in the negative electrode or tin (Sn) as a constituent element in the negative electrode, compared to the case where a carbon material is used for the negative electrode. In the case of using the material contained as a component, the cycle characteristics tended to deteriorate more. That is, when a material containing silicon (Si) as a constituent element is used for the negative electrode or a material containing tin (Sn) as a constituent element is used for the negative electrode, it is expressed by formulas (19) to (22) and formula (24). It has been found that it is particularly effective to use a negative electrode in which a coating containing any one of the above compounds is formed on the surface of the negative electrode active material layer.

  As shown in Table 15, in Example 15-1 to Example 15-5, the discharge capacity retention rate was higher than that in Comparative Example 4-1. That is, in the case where silicon (Si; vapor deposition method) is used for the negative electrode, the film formed on the surface of the positive electrode active material layer is selected from the compounds represented by formula (19) to formula (22) and formula (24). It was found that the cycle characteristics can be improved by including any of them.

  As shown in Table 16, in Example 16-1 to Example 16-5, the discharge capacity retention rate was higher than that of Comparative Example 4-1. That is, when silicon (Si; vapor deposition method) is used for the negative electrode, the film formed on the surface of the separator is any one of the compounds represented by formula (19) to formula (22) and formula (24). It was found that the cycle characteristics can be improved by including.

  In addition, as shown in Table 4, Table 9, Table 15, and Table 16, at least one of the positive electrode, the negative electrode, the separator, and the electrolytic solution contains the compound represented by the formula (1), thereby enabling the cycle. It was found that the characteristics were improved. In this case, it turned out that it is especially effective to use the negative electrode in which the film containing any of the compounds represented by Formula (1) was formed on the surface of the negative electrode active material layer.

  In the compound represented by formula (1), a compound where X = amino group, a compound where X = halogen group, a compound where X = −OM and M = hydrocarbon group, M = Coating a compound that is a group 1 element in a long-period periodic table other than lithium (Li), a compound that is a group 2 element in a long-period periodic table other than M = magnesium (Mg), or a compound that is M = alkylsilyl group Even if they are included in the above, the same results as in the above-mentioned embodiment tend to be obtained. Therefore, in the compound represented by the formula (1), at least one of the negative electrode, the positive electrode, and the separator has X = amino group, X = halogen group, or X = -OM. And M = a compound that is a hydrocarbon group, M = a compound that is a group 1 element in a long-period periodic table other than lithium (Li), and M = a group 2 element in a long-period periodic table other than magnesium (Mg). It can be seen that the cycle characteristics can be improved by including a certain compound or a compound having M = alkylsilyl group.

  The present invention is not limited to the above-described embodiments and examples of the present invention, and various modifications and applications can be made without departing from the gist of the present invention. For example, in the above-described embodiments and examples, a coin-type battery, a cylindrical battery, and a flat battery using a laminate film or the like as an exterior material have been described as examples. However, the present invention is not limited thereto. Instead, for example, various types of shapes and sizes, such as a square battery, can be used.

  In the above-described embodiments and examples, a lithium ion secondary battery has been described as an example, but the present invention can also be applied to other secondary batteries. Examples of the other secondary battery include a so-called metal lithium secondary battery using metal lithium as a negative electrode active material, and a magnesium secondary battery or an aluminum secondary battery that is being studied for practical use. In addition, when applying this invention to a metal lithium secondary battery, at least one of a positive electrode, a separator, and a nonaqueous electrolyte will contain the compound represented by Formula (1). Furthermore, it is applicable not only to a battery with a chemical reaction but also to other electrochemical devices such as an electric double layer capacitor using a positive electrode, a negative electrode, or an electrolytic solution.

  Further, as the non-aqueous electrolyte, a solid polymer electrolyte using an ion conductive polymer or an inorganic solid electrolyte using an ion conductive inorganic material may be used, and these may be used alone or in combination with other electrolytes. May be. Examples of the polymer compound that can be used for the polymer solid electrolyte include polyether, polyester, polyphosphazene, and polysiloxane. Examples of the inorganic solid electrolyte include ion conductive ceramics, ion conductive crystals, and ion conductive glass.

It is sectional drawing showing the structure of the 1st example of the nonaqueous electrolyte battery using the nonaqueous electrolyte by 1st Embodiment of this invention. It is sectional drawing showing the structure of the 2nd example of the nonaqueous electrolyte battery using the nonaqueous electrolyte by 1st Embodiment of this invention. It is sectional drawing which expands and represents a part of winding electrode body shown in FIG. It is sectional drawing showing the structure of the 3rd example of the nonaqueous electrolyte battery using the nonaqueous electrolyte by 1st Embodiment of this invention. It is sectional drawing along the II line of the winding electrode body shown in FIG. It is sectional drawing showing the structure of the negative electrode in 2nd Embodiment of this invention. It is sectional drawing showing the other structure of the negative electrode shown in FIG. It is sectional drawing showing the structure of the negative electrode of a reference example. It is the SEM photograph showing the other cross-section of the negative electrode shown in FIG. 6, and its schematic diagram. It is the SEM photograph showing the other cross-section of the negative electrode shown in FIG. 6, and its schematic diagram. It is sectional drawing showing the structure of the positive electrode in 3rd Embodiment of this invention. It is sectional drawing showing the structure of the separator in 4th Embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 2 ... Positive electrode 2A ... Positive electrode collector 2B ... Positive electrode active material layer 3 ... Separator 4 ... Negative electrode 4A ... Negative electrode collector 4B ... Negative electrode active material layer 5 ....・ Exterior cup 6 ... Exterior can 7 ... Gasket 11 ... Battery can 12, 13 ... Insulating plate 14 ... Battery lid 15 ... Safety valve mechanism 15A ... Disc plate 16 ... Thermal resistance element 17 ... gasket 20 ... wound electrode body 21 ... positive electrode 21A ... positive electrode current collector 21B ... positive electrode active material layer 22 ... negative electrode 22A ... negative electrode current collector Body 22B ... Negative electrode active material layer 23 ... Separator 24 ... Center pin 25 ... Positive electrode lead 26 ... Negative electrode lead 30 ... Winding electrode body 31 ... Positive electrode lead 32 ... Negative electrode lead 33 ... Positive electrode 33A ... Positive electrode current collector 33B ... Electroactive material layer 34 ... Negative electrode 34A ... Negative electrode current collector 34B ... Negative electrode active material layer 35 ... Separator 36 ... Electrolyte layer 37 ... Protective tape 40 ... Exterior member 41 ··· Adhesive film 100 ··· Negative electrode 101 ··· Negative electrode current collector 102 · · · Negative electrode active material layer 103 · · · Coating 201 · · · Negative electrode active material particles 202 and 203 · · · 204A, 204B ... Gap 205 ... Gap 206 ... Metal material 300 ... Positive electrode 301 ... Positive electrode current collector 302 ... Positive electrode active material layer 303 ... Coating 400 ... Separator 401 ... Microporous membrane 402 ... Coating

Claims (16)

A positive electrode and a negative electrode opposed via a separator, and a non-aqueous electrolyte,
At least one of the positive electrode, the negative electrode, the separator, and the nonaqueous electrolyte includes a compound represented by the formula (1).

(R1 to R5 are hydrogen or a substituent. R1 to R5 may be the same, different, or bonded. X is -OM, an amino group, or a halogen group. (It is a group 1 element or a group 2 element in a long-period periodic table, or a hydrocarbon group or an alkylsilyl group, where n = 0 to 4.) The secondary battery according to claim 1, wherein the compound represented by the formula (1) is a compound represented by the formula (2).

(R1 to R5 are hydrogen or a substituent. R1 to R5 may be the same, different, or bonded. X is -OM, an amino group, or a halogen group. It is a group 1 element or a group 2 element in a long-period type periodic table, or a hydrocarbon group or an alkylsilyl group.) The secondary battery according to claim 1, wherein the compound represented by the formula (1) is a compound represented by the formula (3), the formula (4), or the formula (5).

(R1 to R5 are hydrogen or a substituent. R1 to R5 may be the same or different, and may be bonded. N = 0 to 4)

(R1 to R5 are hydrogen or a substituent. R1 to R5 may be the same or different, and may be bonded. N = 0 to 4)

(R1 to R5 are hydrogen or a substituent. R1 to R5 may be the same or different and may be bonded. R6 is a hydrocarbon group. N = 0 to 4. .) The secondary battery according to claim 1, wherein the compound represented by the formula (1) is a compound represented by the formula (6), the formula (7), or the formula (8).

(R1 to R5 are hydrogen or a substituent. R1 to R5 may be the same, different, or bonded.)

(R1 to R5 are hydrogen or a substituent. R1 to R5 may be the same, different, or bonded.)

(R1 to R5 are hydrogen or a substituent. R1 to R5 may be the same or different and may be bonded. R6 is a hydrocarbon group.) The secondary battery according to claim 1, wherein the non-aqueous electrolyte includes a compound represented by the formula (1). The secondary battery according to claim 1, wherein the negative electrode active material layer has a material containing at least one of silicon (Si) and tin (Sn) as a constituent element. The negative electrode has a coating on the negative electrode active material layer provided on the negative electrode current collector,
The secondary battery according to claim 1, wherein the coating includes a compound represented by the formula (1). The secondary battery according to claim 7 , wherein the negative electrode active material layer includes a plurality of negative electrode active material particles and an oxide-containing film that covers a surface of the negative electrode active material particles. The secondary battery according to claim 8 , wherein the oxide-containing film includes at least one oxide of silicon (Si), germanium (Ge), and tin (Sn). The secondary battery according to claim 7, wherein the negative electrode active material layer includes a plurality of negative electrode active material particles and a metal material that does not alloy with the electrode reactant in a gap between the negative electrode active material particles. The secondary battery according to claim 10 , wherein the metal material is at least one of iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), and copper (Cu). The positive electrode has a film on the positive electrode active material layer provided on the positive electrode current collector,
The secondary battery according to claim 1, wherein the coating includes a compound represented by Formula (1). The separator has a coating on its surface,
The secondary battery according to claim 1, wherein the coating includes a compound represented by the formula (1). A positive electrode and a negative electrode which is opposed via a separator, in the secondary battery including a non-aqueous electrolyte, a,
A method for producing a secondary battery, wherein the compound represented by formula (1) is contained in at least one of the positive electrode, the negative electrode, the separator, and the nonaqueous electrolyte.

(R1 to R5 are hydrogen or a substituent. R1 to R5 may be the same, different, or bonded. X is -OM, an amino group, or a halogen group. (It is a group 1 element or a group 2 element in a long-period periodic table, or a hydrocarbon group or an alkylsilyl group, where n = 0 to 4.) The positive electrode has a positive electrode active material layer on a positive electrode current collector, the negative electrode has a negative electrode active material layer on a negative electrode current collector,
Using a solution containing the compound represented by the formula (1), at least one surface of the positive electrode active material layer, the negative electrode active material layer, and the separator is represented by the formula (1). The method for producing a secondary battery according to claim 14 , wherein a film containing the compound is formed. At least one of the positive electrode active material layer, the negative electrode active material layer and the separator is immersed in a solution containing the compound represented by the formula (1), or represented by the formula (1). The method for producing a secondary battery according to claim 15, wherein a solution containing the compound is applied to at least one surface of the positive electrode active material layer, the negative electrode active material layer, and the separator.

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